CN105524349B - A kind of low VOC polypropylene resin composites and preparation method thereof - Google Patents
A kind of low VOC polypropylene resin composites and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of low VOC polypropylene resin composites of plastic applications and preparation method thereof.The low VOC polypropylene resin composites, include the following components of blending：Polypropylene, VOC inhibitor；Wherein, counted by 100 parts by weight of polypropylene, the VOC inhibitor is 0.1~10 parts by weight；The VOC inhibitor is made up of the component of the following percentage composition meter for accounting for VOC inhibitor gross weights：Fully sulfurized silicon rubber powder 0wt%~80wt%, Cellulose nanocrystal body 20wt%~100wt%；The rubber particles average grain diameter of the fully sulfurized silicon rubber powder is 0.05~1 μm, and it has cross-linked structure, and gel content is 60wt% or higher.Cellulose nanocrystal body BET specific surface area is 100~350m2/ g, surface charge density is 0.1~0.4e/nm2, length is 90~300nm, and width is 5~15nm.The low VOC polypropylene resin composites of the present invention, the method compounded by VOC inhibitor and acid-acceptor, the VOC content of polypropene composition is significantly reduced, operating procedure is simple, it is adaptable to the field such as the higher superior automobile inside gadget of environmental requirement, medical and packaging material for food.
Description
Technical field
The present invention relates to a kind of polypropylene resin composite of plastic applications, further say, be to be related to a kind of low VOC to gather
Propylene resin composition and preparation method thereof.
Background technology
The advantages of polypropylene (PP) is because of its high comprehensive performance, wide material sources and super quality and competitive price, are widely used to people
The every field of life.But it is dirty all to there is release volatile organic matter (VOC) to some extent in existing polypropylene material and product
The problem of contaminating environment and healthy harm people, it is higher in environmental requirement which greatly limits polypropylene material
The application in the fields such as superior automobile inside gadget, medical and packaging material for food.Therefore, the low VOC polypropylene of environment-friendly type is researched and developed
Resin and material can expand PP application field and meet the requirement of green material.
At present, the report on the research of low VOC polypropylene materials is more, and they are mostly using chemical reaction, physical absorption
And melt devolatilization technology distributes problem improve VOC in original polypropylene material.Such as Chinese patent (CN 101570612A)
VOC content is reduced by adding a kind of inorganic photochemical catalyst decomposition organic molecule, but its effect is limited.Chinese patent
(CN101255252A) VOC of material is reduced by adding organic matter expellent such as isopropanol/water, but this mode is present
Compatibility and persistent problem.It is low that European patent (EP 1988122A1) uses metallocene polypropylene resins to be prepared for matrix resin
VOC automotive interior material；European patent (EP 2154190A1) is prepared using specific light stabilizer such as light stabilizer 119
The PP composite material of low VOC content；Chinese patent (CN 101691435A) is by using being total to that specific hydrogen-regulating method is produced
Poly- polypropylene produces low VOC PP composite material.Foregoing invention is often changed just for some factor for producing VOC
It is kind, the problem of VOC of various factors generation can not be solved simultaneously.And physical absorption can inhale to all small molecules that PP is produced
Attached, addition physical absorbent is conventional method.As Chinese patent (CN 1727389A, CN 1727390A) is disclosed using thin
Hole silica gel and molecular sieve reduce the smell of material and the volatilization problems of organic compound, Chinese patent as adsorbent
(CN102276921A) disclose and use string to reduce the odor problem of polypropylene material as adsorbent.Above-mentioned use is inhaled
Although attached agent method can play a role to reduction polypropylene VOC, the problem of still there is adsorption equilibrium, higher
At a temperature of balance direction movement to desorption, there is the hidden danger that the polypropylene material VOC later stages discharge again.Further, since absorption
The adsorption efficiency of agent, itself still deposited the problems such as scattered in polypropylene matrix with polyacrylic compatibility and adsorbent
.Accordingly, it would be desirable to a kind of polypropylene resin composite with low VOC content.
The content of the invention
To solve the above-mentioned problems in the prior art, this invention address that providing a kind of low VOC acrylic resins group
Compound and preparation method thereof.Wait not enough for VOC content in existing polypropylene material is higher, the present invention is led to first from source
Chemical reaction is crossed to distribute to reduce or suppress the VOC produced by acid catalysis degradation of polypropylene；Efficient cellulose is selected in addition
Nanocrystal is carried out pointedly adsorbing and being chemically bonded to VOC in polypropylene, and nanometer powder silicon rubber is given full play in addition
It is good to assist dispersion effect, adsorption efficiency is greatly improved, distributing for VOC in polypropylene is significantly reduced.
An object of the present invention is to provide a kind of low VOC polypropylene resin composites, includes the following components of blending：
Polypropylene, VOC inhibitor；
Wherein, counted by 100 parts by weight of polypropylene, the VOC inhibitor is 0.1~10 parts by weight, preferably 0.1~5
Parts by weight, more preferably 0.2~5 parts by weight；
Heretofore described polypropylene includes various types of acrylic resins disclosed in prior art, including homopolymerization
Polypropylene and acrylic resin copolymer etc..
The VOC inhibitor includes following components：Fully sulfurized silicon rubber powder, Cellulose nanocrystal body；Wherein, to account for
The percentage composition meter of VOC inhibitor gross weights, fully sulfurized silicon rubber powder be 0wt%~80wt%, preferably 0wt%~
60wt%, more preferably 20wt%~60wt%；Cellulose nanocrystal body be 20wt%~100wt%, preferably 40wt%~
100wt%, more preferably 40wt%~80wt%.
The fully sulfurized silicon rubber powder, its rubber particles average grain diameter be 0.05~1 μm, preferably 0.05~0.2 μm, more
Preferably 0.05~0.1 μm；Its rubber particles has cross-linked structure, and gel content is 60wt% or higher, preferably 75wt%
Or higher, more preferably 90wt% or higher.The fully sulfurized silicon rubber powder particle preferably has the full vulcanization of equal phase structure
Each particulate in silicon rubber powder, the i.e. fully sulfurized silicon rubber powder is homogeneous, and single particulate is all in composition
Homogeneous.Do not have to find the not homogeneous phenomenons such as layering, split-phase in particulate under the observation of existing microtechnic.The powdered rubber
By the way that corresponding rubber latex cross-linking radiation is fixed rubber particles particle diameter.Form of finely divided powder, mehtod silicon of the present invention
Detailed content of rubber and preparation method thereof, reference can be made to the present invention is incorporated herein in Chinese patent CN 1383439A, entire contents
It is used as reference.
The Cellulose nanocrystal body has big BET specific surface area, and BET specific surface area is 100~350m2/ g, preferably
150~300m2/g.BET is three scientists Brunauer, Emmett and Teller acronym, and BET specific surface area is
The characterization parameter set up on the basis of the multi-molecular absorption formula that this three scientists derive from classical statistical theory, BET
Specific surface area has been widely used in the Data processing of particle surface Study on adsorption properties and coherent detection instrument.Cellulose is received
The optional Cellulose nanocrystal bodies commonly used in the prior art of meter Jing Ti, specific preferably wood-cellulose nanocrystal.The present invention
Wood-cellulose nanocrystal can using following methods prepare：It is first depending on GB/T 2677.6-1994, GB/T 2677.8-
1994, GB/T 2677.10-1995 method successively removes extract, lignin and hemicellulose in timber, freeze-drying
Method obtains cellulose sample, then according to document (Derek G Gray.Effect of Reaction Conditions on
the Properties and Behavior of Wood Cellulose Nanocrystal Suspensions[J]
.Biomacromolecules.2005,6(2):1048-1054.) in method prepare wood-cellulose nanocrystal.Specifically
Preparation method includes：
1st, wood pulp wears into 40 mesh cellulose powders by beveller；
2nd, cellulose powder is added in 64wt% aqueous sulfuric acids with certain sulfuric acid/cellulose rate of charge, 45 DEG C of stirrings
Lower reaction certain time；Wherein, sulfuric acid/cellulose rate of charge optional 5~20mL/g, preferably 5~15mL/g；Reaction time can be
30~60 minutes.
3rd, the deionized water of 10 times of volumes is toppled over into reaction solution, hydrolysis is terminated.
4th, multiple centrifugal treating previous step solution, topples over upper solution to remove sulfuric acid molecule.Specifically, centrifugation turns every time
Optional 10000rpm/min of speed or so, the optional 15min of centrifugation time.Centrifugation is repeatable 3 times.
5th, the bag filter for 12000~14000 molecular cut offs of solid that centrifugation is obtained, several days of dialysis treatment in water
(generally 3 days) are until dialyzate pH is constant.
6th, in ice-water bath, the ultrasonically treated about 7min of dialyzate is to obtain wood-cellulose nanocrystal solution.Wherein, it is ultrasonic
The optional 40kHz of ultrasonic wave of processing, 215W power.
7th, hybrid resin bed (specifically optional TMD-8 hydrogen and hydrogen-oxygen type, Aldrich) immersion 24~48 hours, after filtering,
Obtain wood-cellulose nanocrystal solution.
8th, freeze-drying process wood-cellulose nanocrystal solution, obtains wood-cellulose nanocrystal.Wherein, freeze
The condenser temperature of drying process is chosen as drying process under -54 DEG C, vacuum condition；Processing time can be 4 days.
The described Cellulose nanocrystal body surface density of surface charge is 0.1~0.4e/nm2, preferably 0.2~0.3e/nm2；Length
For 90~300nm, preferably 100~200nm；Width is 5~15nm.
The present invention may also include acid-acceptor, be counted by 100 parts by weight of polypropylene, and the acid-acceptor is 0.05~1 weight
Part, preferably 0.1~0.6 parts by weight.Acid-acceptor of the present invention, main character is that it has alkalescence, can be residual with acid catalyst
Excess, which reacts, plays neutralization, the present invention required for acid-acceptor should simultaneously can in polypropylene fine dispersion.This hair
Bright acid-acceptor can select in metal oxide, lactate, benzoate, silicate and stearate containing Na, Ca, Zn extremely
Few one kind, the preferably stearate containing Na, Ca, Zn.Wherein metal oxide preferably is selected from least one in calcium oxide, zinc oxide
Kind；The silicate is preferably selected from natural or synthetic hydrotalcite；The stearate containing Na, Ca, Zn preferably is selected from stearic acid
At least one of calcium, zinc stearate, odium stearate.
Further, also include resisting in the effect for suppressing VOC, polypropene composition of the present invention to reach to improve
Oxygen agent, antioxidant and fully sulfurized silicon rubber powder have preferably collaboration dispersion effect, can effectively reduce VOC in polypropylene and contain
Amount.Antioxidant can select the various antioxidant commonly used in prior art polypropylene, and total consumption of antioxidant is using polypropylene as 100 weights
Number meter is measured, is 0.1~0.5 parts by weight, preferably 0.15~0.3 parts by weight.
The mixture of the preferred Hinered phenols antioxidant of described antioxidant and phosphoric acid ester antioxidant.The Hinered phenols resist
The weight ratio of oxygen agent and phosphoric acid ester antioxidant can be 1:(1~4), preferably 1:(1~3), more preferably 1：(1~2).
The Hinered phenols antioxidant may be selected from four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythrites
Ester, β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyls) propionic acid, N, N'- couples-(3- (3,5- di-t-butyl -4- hydroxyls
Base phenyl) propiono) hexamethylene diamine, at least one of 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid；Institute
State phosphoric acid ester antioxidant and be selected from three (2,4- di-tert-butylphenols) phosphite esters, double (2,4- DI-tert-butylphenol compounds) pentaerythrites two
At least one of phosphite ester.
Specifically, the Hinered phenols antioxidant may be selected from：The anti-oxidant Irganox of Ciba fine chemicals' production
1010【Four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters】、Irganox 1076【β-(the uncles of 3,5- bis-
Butyl -4- hydroxy phenyls) the positive octadecanol ester of propionic acid】、Irganox 1098【N, N'- pairs-(3- (3,5- di-t-butyl -4- hydroxyls
Base phenyl) propiono) hexamethylene diamine】、Irganox 3114【1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanide is urinated
Acid】, or the antioxidant 1010 that BASF Aktiengesellschaft produces【Four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] seasons
Doutrate】Deng；The phosphoric acid ester antioxidant may be selected from：Irgafos168【Three (2,4- di-tert-butylphenols) phosphite esters】、
Irganox 626【Double (2,4- DI-tert-butylphenol compounds) pentaerythritol diphosphites】Or BASF Aktiengesellschaft's production is anti-
Oxygen agent 168【Three (2,4- di-tert-butylphenols) phosphite esters】Deng.
In addition, in the process of polypropene composition of the present invention, can be according to specific processing the need for, in blending material
It is middle to add the processing aid commonly used in acrylic resin modification technology, for example：Lubricant, antistatic additive, dispersant, pigment etc.,
Its consumption is conventional amount used, or is adjusted according to the requirement of actual conditions.
The second object of the present invention is the preparation method for providing the low VOC polypropylene composition, can pass through following skill
Art scheme is realized：It will be well mixed comprising the component including the polypropylene, VOC inhibitor by the content, melt blending
Described low VOC polypropylene resin composites are made.
The preparation method of this kind of polypropene composition is further illustrated, is comprised the following steps：
1st step：The Cellulose nanocrystal body and the fully sulfurized silicon rubber powder are sufficiently mixed according to the ratio
Obtain the VOC inhibitor；
2nd step：By each component including VOC inhibitor obtained as above, the dried acrylic resin
It is well mixed by the content in mixing apparatus, it is preferably dry-mixed 3~5 minutes, obtain pre-composition；
3rd step：The low VOC polypropylene resin composites will be obtained after the pre-composition melt blending extruding pelletization.For
More preferable removing VOC, this step preferably keeps the vacuum of device vacuum system more than -0.05MPa, more preferably -
More than 0.08MPa.
In the process of low VOC polypropylene resin composites of the present invention, material melts blending temperature is
Blending temperature used in usual polypropylene processing, it should in the model for not only ensureing matrix resin melting completely but also will not decomposing it
Interior selection is enclosed, generally 190 DEG C~230 DEG C, processing temperature preferably is 190~220 DEG C；The screw speed of melt blending equipment
For 300~450rpm.
The mixing apparatus of material can be using various batch mixings used in the prior art in the preparation method of the invention described above
Equipment, such as mixer, kneading machine.Melt blending equipment used in the above method of the present invention is in rubber and plastic processing industry
General blending equipment, can be double screw extruder, BUSS mixing units etc..
Compared with prior art, the present invention has the advantages that：
1. the present invention is reacted with diluted acid relict catalyst present in polypropylene using acid-acceptor, play reduce or
Suppression produces VOC effect because of the degraded of diluted acid catalyzed polypropylene.
2. on the one hand Cellulose nanocrystal body remains in VOC in polypropylene using the effectively absorption of larger specific surface area；Separately
One side forms interaction of hydrogen bond using the active group hydroxy functional group on its surface and the micromolecular compound of aldoketones, effectively
Aldoketones is adsorbed, effectively suppresses aldoketones VOC.Therefore reduction polypropylene VOC rate of release, delays or prevents in polypropylene
VOC discharge.
3. fully sulfurized silicon rubber powder and Cellulose nanocrystal body compounding can effectively improve the latter in acrylic resin
Dispersion effect, improve the adsorption efficiency of Cellulose nanocrystal body, significantly reduce in polypropylene VOC and discharge content；And full sulphur
Changing silicon rubber powder, nano-dispersed can also adsorb VOC remaining in polypropylene to a certain extent certainly in acrylic resin, prolong
Delay its release.
The total volatile organism (TVOC) of polypropene composition of the present invention can be significantly reduced, more preferably, and TVOC can be with
Less than 50 μ gC/g, the deficiencies in the prior art are solved well, and operating procedure is simple and reliable, and input cost is relatively low, it is adaptable to
The fields such as the higher superior automobile inside gadget of environmental requirement, medical and packaging material for food.
Embodiment
The present invention is specifically described with reference to specific embodiment, it is necessary to it is pointed out here that be following examples
It is served only for further illustrating the present invention, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art's root
Some the nonessential modifications and adaptations made according to present invention to the present invention still belong to protection scope of the present invention.
Embodiment 1~6
Cellulose nanocrystal body (the average BET specific surface area 250m2/ g, average length 150nm, mean breadth 9nm,
Average surface charge density 0.2e/nm2, China Forestry Science Research Institute) and the fully sulfurized silicon rubber powder (trade mark VP-
602,0.1 μm of average grain diameter, gel content 90wt%；Beijing Chemical Research Institute) it is sufficiently mixed and obtains the VOC inhibitor；Again
By the obtained VOC inhibitor and COPP (K9020, Sinopec Beijing Yanshan Mountain branch company), acid-acceptor (stearic acid
Calcium, Tianjin Gang Chang Chemical Co., Ltd.s), antioxidant (antioxidant 1010, belongs to Hinered phenols antioxidant, chemistry entitled four [β-
(3,5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and irgasfos 168, belong to phosphoric acid ester antioxidant, change
Scientific name is three (2,4- di-tert-butylphenol) phosphite esters, and the weight ratio of antioxidant 1010 and irgasfos 168 is 1:2, both come from
BASF Aktiengesellschaft) it is put into homogenizer, stirred 3 minutes under 300 revs/min of rotating speed, be sufficiently mixed each component
Uniformly；Said mixture material then is kneaded into unit by the BUSS in the range of 190 DEG C~220 DEG C, and (MKD-30, Switzerland BUSS are public
Department), the extruding pelletization under conditions of vacuum -0.08MPa is kept obtains low VOC polypropylene resin composites.Its specific formula
1 is shown in Table, wherein each component content is in terms of parts by weight.
The pellet of extrusion is dried into 2h in 80 DEG C of constant temperature ovens, TVOC test is according to the meeting of German automobiles industrial combination
Standard VDA277 is tested.Specific performance the results are shown in Table 1.
The preparation method of wherein Cellulose nanocrystal body is：According to GB/T 2677.6-1994, GB/T2677.8-1994,
GB/T 2677.10-1995 successively remove extract, lignin and hemicellulose in timber, and freeze-drying obtains cellulose
Sample, method (Biomacromolecules.2005,6 (2) then reported according to Gray D.G.:1048-1054.) prepare
Cellulose nanocrystal body.
Specific steps include：1st, wood pulp wears into 40 mesh cellulose powders by beveller；2nd, cellulose powder with
15mL/g sulfuric acid/cellulose rate of charge is added in 64wt% aqueous sulfuric acids, the lower reaction 30min of 45 DEG C of stirrings.3rd, to reaction
The deionized water of 10 times of volumes is toppled in liquid, hydrolysis is terminated.4th, centrifugal treating (centrifugal rotational speed is 10000rpm/min, from
Heart time 15min) previous step solution, upper solution is toppled over to remove sulfuric acid molecule, and this step is repeated 3 times.5th, centrifugation is obtained
The bag filter of 12000~14000 molecular cut offs of solid, dialysis treatment 3 days in water, until dialyzate pH is constant.6th, ice
In water-bath, ultrasonically treated (ultrasonic wave be 40kHz, the 215W power under) 7min of dialyzate is molten to obtain wood-cellulose nanocrystal
Liquid.7th, hybrid resin bed (TMD-8 hydrogen and hydrogen-oxygen type, Aldrich) soaks 24~48 hours, after filtering, obtains wood-cellulose
Nanocrystal solution.8th, freeze-drying process (condenser temperature is drying process under -54 DEG C, vacuum condition) wood-cellulose nanometer
Crystalloid solution 4 days, obtains wood-cellulose nanocrystal.
Embodiment 7
By the Cellulose nanocrystal body (average BET specific surface area 300m2/ g, average length 100nm, mean breadth
7nm, average surface charge density 0.3e/nm2, China Forestry Science Research Institute, in its specific preparation method and embodiment 1~6
Only in step 2 45 DEG C of the preparation method of the Cellulose nanocrystal body stirring lower reaction time are different, are 45min, other steps with
The preparation method of Cellulose nanocrystal body is consistent in embodiment 1~6) and the fully sulfurized silicon rubber powder (trade mark VP-602, it is flat
Equal 0.05 μm of particle diameter, gel content 75wt%；Beijing Chemical Research Institute) it is sufficiently mixed and obtains the VOC inhibitor；It will obtain again
The VOC inhibitor and COPP (K9020, Sinopec Beijing Yanshan Mountain branch company), acid-acceptor (calcium stearate, day
The prosperous Chemical Co., Ltd. in PORT OF JINSHI), (antioxidant 1010, belongs to Hinered phenols antioxidant to antioxidant, the entitled four [β-(3,5- of chemistry
Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and irgasfos 168, belong to phosphoric acid ester antioxidant, chemistry is entitled
The weight ratio of three (2,4- di-tert-butylphenol) phosphite esters, antioxidant 1010 and irgasfos 168 is 1:2, both come from German bar
Si Fu companies) it is put into homogenizer, stirred 3 minutes under 300 revs/min of rotating speed, each component is sufficiently mixed uniformly；With
Said mixture material is kneaded into unit (MKD-30, BUSS companies of Switzerland) by the BUSS in the range of 190 DEG C~220 DEG C afterwards,
Extruding pelletization under conditions of vacuum -0.08MPa is kept, low VOC polypropylene resin composites are obtained.Its specific formula is shown in Table 1,
Wherein each component content is in terms of parts by weight.
The pellet of extrusion is dried into 2h in 80 DEG C of constant temperature ovens, TVOC test is according to the meeting of German automobiles industrial combination
Standard VDA277 is tested.Specific performance the results are shown in Table 1.
Embodiment 8
By the Cellulose nanocrystal body (average BET specific surface area 100m2/ g, average length 300nm, mean breadth
15nm, average surface charge density 0.1e/nm2, China Forestry Science Research Institute, in its specific preparation method and embodiment 1~6
Only sulfuric acid/cellulose rate of charge is different in step 2 for the preparation method of Cellulose nanocrystal body, is 8.75mL/g, other steps
It is consistent with the preparation method of Cellulose nanocrystal body in embodiment 1~6) and the fully sulfurized silicon rubber powder (trade mark VP-602,
1 μm of average grain diameter, gel content 60wt%；Beijing Chemical Research Institute) it is sufficiently mixed and obtains the VOC inhibitor；It will obtain again
The VOC inhibitor and COPP (K9020, Sinopec Beijing Yanshan Mountain branch company), acid-acceptor (calcium stearate, day
The prosperous Chemical Co., Ltd. in PORT OF JINSHI), (antioxidant 1010, belongs to Hinered phenols antioxidant to antioxidant, the entitled four [β-(3,5- of chemistry
Di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, and irgasfos 168, belong to phosphoric acid ester antioxidant, chemistry is entitled
The weight ratio of three (2,4- di-tert-butylphenol) phosphite esters, antioxidant 1010 and irgasfos 168 is 1:2, both come from German bar
Si Fu companies) it is put into homogenizer, stirred 3 minutes under 300 revs/min of rotating speed, each component is sufficiently mixed uniformly；With
Said mixture material is kneaded into unit (MKD-30, BUSS companies of Switzerland) by the BUSS in the range of 190 DEG C~220 DEG C afterwards,
Extruding pelletization under conditions of vacuum -0.08MPa is kept, low VOC polypropylene resin composites are obtained.Its specific formula is shown in Table 1,
Wherein each component content is in terms of parts by weight.
The pellet of extrusion is dried into 2h in 80 DEG C of constant temperature ovens, TVOC test is according to the meeting of German automobiles industrial combination
Standard VDA277 is tested.Specific performance the results are shown in Table 1.
Embodiment 9
By the Cellulose nanocrystal body (average BET specific surface area 200m2/ g, average length 200nm, mean breadth
8nm, average surface charge density 0.2e/nm2, China Forestry Science Research Institute, in its specific preparation method and embodiment 1~6
Sulfuric acid/cellulose rate of charge is different in step 2 for the preparation method of Cellulose nanocrystal body, is 8.75mL/g, under 45 DEG C of stirrings
Reaction time is different, is 60min, other steps are consistent with the preparation method of Cellulose nanocrystal body in embodiment 1~6) and institute
State fully sulfurized silicon rubber powder (trade mark VP-602,0.2 μm of average grain diameter, gel content 80wt%；Beijing Chemical Research Institute) fill
Divide and be mixed to get the VOC inhibitor；Again by the obtained VOC inhibitor and COPP (K9020, Sinopec north
Flycatcher mountain branch company), acid-acceptor (calcium stearate, Tianjin Gang Chang Chemical Co., Ltd.s), (antioxidant 1010 belongs to antioxidant
Hinered phenols antioxidant, entitled four [β-(3, the 5- di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester of chemistry, and antioxygen
Agent 168, belongs to phosphoric acid ester antioxidant, entitled three (2,4- di-tert-butylphenol) phosphite ester, antioxidant 1010 and the antioxygens of chemistry
The weight ratio of agent 168 is 1:2, both come from BASF Aktiengesellschaft) it is put into homogenizer, under 300 revs/min of rotating speed
Stirring 3 minutes, makes each component be sufficiently mixed uniformly；Then by said mixture material by the BUSS in the range of 190 DEG C~220 DEG C
Unit (MKD-30, BUSS companies of Switzerland) is kneaded, the extruding pelletization under conditions of vacuum -0.08MPa is kept obtains low VOC
Polypropylene resin composite.Its specific formula is shown in Table 1, and wherein each component content is in terms of parts by weight.
The pellet of extrusion is dried into 2h in 80 DEG C of constant temperature ovens, TVOC test is according to the meeting of German automobiles industrial combination
Standard VDA277 is tested.Specific performance the results are shown in Table 1.
Embodiment 10
By the Cellulose nanocrystal body (average BET specific surface area 350m2/ g, average length 90nm, mean breadth 5nm,
Average surface charge density 0.4e/nm2, China Forestry Science Research Institute, fiber in its specific preparation method and embodiment 1~6
The only in step 2 45 DEG C stirring lower reaction time of the preparation method of plain nanocrystal are different, are 60min, other steps are with implementing
The preparation method of Cellulose nanocrystal body is consistent in example 1~6) and the fully sulfurized silicon rubber powder (trade mark VP-602, average grain
0.1 μm of footpath, gel content 90wt%；Beijing Chemical Research Institute) it is sufficiently mixed and obtains the VOC inhibitor；Again by obtained institute
State VOC inhibitor and COPP (K9020, Sinopec Beijing Yanshan Mountain branch company), acid-acceptor (calcium stearate, Tianjin
Gang Chang Chemical Co., Ltd.s), (antioxidant 1010, belongs to Hinered phenols antioxidant to antioxidant, the entitled four [β-(3,5- bis- uncles of chemistry
Butyl -4- hydroxy phenyls) propionic acid] pentaerythritol ester, and irgasfos 168, belong to phosphoric acid ester antioxidant, chemistry entitled three
The weight ratio of (2,4- di-tert-butylphenol) phosphite ester, antioxidant 1010 and irgasfos 168 is 1:2, both come from German Bath
Husband company) it is put into homogenizer, stirred 3 minutes under 300 revs/min of rotating speed, each component is sufficiently mixed uniformly；Then
By said mixture material by the BUSS mixing units (MKD-30, BUSS companies of Switzerland) in the range of 190 DEG C~220 DEG C, protecting
Extruding pelletization under conditions of vacuum -0.08MPa is held, low VOC polypropylene resin composites are obtained.Its specific formula is shown in Table 1, its
Middle each component content is in terms of parts by weight.
The pellet of extrusion is dried into 2h in 80 DEG C of constant temperature ovens, TVOC test is according to the meeting of German automobiles industrial combination
Standard VDA277 is tested.Specific performance the results are shown in Table 1.
Comparative example 1~4
By with the COPP of the identical source of embodiment 1~10, fully sulfurized silicon rubber powder, Cellulose nanocrystal body,
The raw materials such as acid-acceptor (calcium stearate), adsorbent (RS378, German Dao Xu high polymer materials Co., Ltd), antioxidant are by table 1
Specific proportioning is weighed, and is respectively put into homogenizer, is stirred 3 minutes under 300 revs/min of rotating speed, each component is fully mixed
Close uniform.Said mixture material is then kneaded into unit by the BUSS in the range of 190 DEG C~220 DEG C, keep vacuum-
Extruding pelletization under conditions of 0.08MPa, obtains polypropene composition.Its specific formula is shown in Table 1, and wherein each component content is with weight
Measure number meter.
The pellet of extrusion is dried into 2h in 80 DEG C of constant temperature ovens, TVOC test is according to the meeting of German automobiles industrial combination
Standard VDA277 is tested.Specific performance the results are shown in Table 1.
The embodiment 1~10 of table 1, the component proportion of comparative example 1~4 and the performance test results
Embodiment 11~16
By the Cellulose nanocrystal body (average BET specific surface area 250m2/ g, average length 110nm, mean breadth
8nm, average surface charge density 0.3e/nm2, China Forestry Science Research Institute, in its specific preparation method and embodiment 1~6
Only in step 2 45 DEG C of the preparation method of the Cellulose nanocrystal body stirring lower reaction time are different, are 40min, other steps with
The preparation method of Cellulose nanocrystal body is consistent in embodiment 1~6) and the fully sulfurized silicon rubber powder (trade mark VP-602, it is flat
Equal 0.1 μm of particle diameter, gel content 90wt%；Beijing Chemical Research Institute) it is sufficiently mixed and obtains the VOC inhibitor；It will obtain again
The VOC inhibitor and HOPP (K1712, Sinopec Beijing Yanshan Mountain branch company), acid-acceptor (zinc stearate, day
The prosperous Chemical Co., Ltd. in PORT OF JINSHI), (antioxidant 1076 belongs to Hinered phenols antioxidant, chemical entitled β-(3,5- bis- to antioxidant
Tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, and irgasfos 168, belong to phosphoric acid ester antioxidant, chemistry is entitled
The weight ratio of three (2,4- di-tert-butylphenol) phosphite esters, antioxidant 1076 and irgasfos 168 is 1:2, both come from German bar
Si Fu companies) it is put into homogenizer, stirred 3 minutes under 300 revs/min of rotating speed, each component is sufficiently mixed uniformly；With
Said mixture material is kneaded into unit (MKD-30, BUSS companies of Switzerland) by the BUSS in the range of 190 DEG C~220 DEG C afterwards,
Extruding pelletization under conditions of vacuum -0.08MPa is kept, low VOC polypropylene resin composites are obtained.Its specific formula is shown in Table 2,
Wherein each component content is in terms of parts by weight.
The pellet of extrusion is dried into 2h in 80 DEG C of constant temperature ovens, TVOC test is according to the meeting of German automobiles industrial combination
Standard VDA277 is tested.Specific performance the results are shown in Table 2.
Embodiment 17
By the Cellulose nanocrystal body (average BET specific surface area 150m2/ g, average length 250nm, mean breadth
11nm, average surface charge density 0.2e/nm2, China Forestry Science Research Institute, in its specific preparation method and embodiment 1~6
Sulfuric acid/cellulose rate of charge is different in step 2 for the preparation method of Cellulose nanocrystal body, is 8.75mL/g, under 45 DEG C of stirrings
Reaction time is different, is 45min, other steps are consistent with the preparation method of Cellulose nanocrystal body in embodiment 1~6) and institute
State fully sulfurized silicon rubber powder (trade mark VP-602,0.1 μm of average grain diameter, gel content 90wt%；Beijing Chemical Research Institute) fill
Divide and be mixed to get the VOC inhibitor；Again by the obtained VOC inhibitor and HOPP (K1712, Sinopec north
Flycatcher mountain branch company), acid-acceptor (zinc stearate, Tianjin Gang Chang Chemical Co., Ltd.s), (antioxidant 1076 belongs to antioxidant
Hinered phenols antioxidant, the chemical entitled β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, and antioxidant
168, belong to phosphoric acid ester antioxidant, entitled three (2,4- di-tert-butylphenol) phosphite ester, antioxidant 1076 and the antioxidant of chemistry
168 weight ratio is 1:2, both come from BASF Aktiengesellschaft) it is put into homogenizer, stirred under 300 revs/min of rotating speed
Mix 3 minutes, each component is sufficiently mixed uniformly；Then said mixture material is mixed by the BUSS in the range of 190 DEG C~220 DEG C
Mill group (MKD-30, BUSS companies of Switzerland), the extruding pelletization under conditions of vacuum -0.08MPa is kept obtains low VOC and gathered
Propylene resin composition.Its specific formula is shown in Table 2, and wherein each component content is in terms of parts by weight.
The pellet of extrusion is dried into 2h in 80 DEG C of constant temperature ovens, TVOC test is according to the meeting of German automobiles industrial combination
Standard VDA277 is tested.Specific performance the results are shown in Table 2.
Embodiment 18
By the Cellulose nanocrystal body (average BET specific surface area 300m2/ g, average length 120nm, mean breadth
8nm, average surface charge density 0.3e/nm2, China Forestry Science Research Institute, in its specific preparation method and embodiment 1~6
Sulfuric acid/cellulose rate of charge is different in step 2 for the preparation method of Cellulose nanocrystal body, is 10mL/g, anti-under 45 DEG C of stirrings
It is different between seasonable, be 60min, other steps are consistent with the preparation method of Cellulose nanocrystal body in embodiment 1~6) and it is described
Fully sulfurized silicon rubber powder (trade mark VP-602,0.1 μm of average grain diameter, gel content 90wt%；Beijing Chemical Research Institute) fully
It is mixed to get the VOC inhibitor；Again by the obtained VOC inhibitor and HOPP (K1712, Sinopec Beijing
Yanshan Mountain branch company), acid-acceptor (zinc stearate, Tianjin Gang Chang Chemical Co., Ltd.s), antioxidant (antioxidant 1076, belong to by
Hinder phenolic antioxidant, the chemical entitled β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, and antioxidant
168, belong to phosphoric acid ester antioxidant, entitled three (2,4- di-tert-butylphenol) phosphite ester, antioxidant 1076 and the antioxidant of chemistry
168 weight ratio is 1:2, both come from BASF Aktiengesellschaft) it is put into homogenizer, stirred under 300 revs/min of rotating speed
Mix 3 minutes, each component is sufficiently mixed uniformly；Then said mixture material is mixed by the BUSS in the range of 190 DEG C~220 DEG C
Mill group (MKD-30, BUSS companies of Switzerland), the extruding pelletization under conditions of vacuum -0.08MPa is kept obtains low VOC and gathered
Propylene resin composition.Its specific formula is shown in Table 2, and wherein each component content is in terms of parts by weight.
The pellet of extrusion is dried into 2h in 80 DEG C of constant temperature ovens, TVOC test is according to the meeting of German automobiles industrial combination
Standard VDA277 is tested.Specific performance the results are shown in Table 2.
Embodiment 19
By the Cellulose nanocrystal body (average BET specific surface area 250m2/ g, average length 130nm, mean breadth
8nm, average surface charge density 0.3e/nm2, China Forestry Science Research Institute, in its specific preparation method and embodiment 1~6
Sulfuric acid/cellulose rate of charge is different in step 2 for the preparation method of Cellulose nanocrystal body, is 10mL/g, anti-under 45 DEG C of stirrings
It is different between seasonable, be 45min, other steps are consistent with the preparation method of Cellulose nanocrystal body in embodiment 1~6) and it is described
Fully sulfurized silicon rubber powder (trade mark VP-602,0.05 μm of average grain diameter, gel content 90wt%；Beijing Chemical Research Institute) fully
It is mixed to get the VOC inhibitor；Again by the obtained VOC inhibitor and HOPP (K1712, Sinopec Beijing
Yanshan Mountain branch company), acid-acceptor (zinc stearate, Tianjin Gang Chang Chemical Co., Ltd.s), antioxidant (antioxidant 1076, belong to by
Hinder phenolic antioxidant, the chemical entitled β-positive octadecanol ester of (3,5- di-tert-butyl-hydroxy phenyl) propionic acid, and antioxidant
168, belong to phosphoric acid ester antioxidant, entitled three (2,4- di-tert-butylphenol) phosphite ester, antioxidant 1076 and the antioxidant of chemistry
168 weight ratio is 1:2, both come from BASF Aktiengesellschaft) it is put into homogenizer, stirred under 300 revs/min of rotating speed
Mix 3 minutes, each component is sufficiently mixed uniformly；Then said mixture material is mixed by the BUSS in the range of 190 DEG C~220 DEG C
Mill group (MKD-30, BUSS companies of Switzerland), the extruding pelletization under conditions of vacuum -0.08MPa is kept obtains low VOC and gathered
Propylene resin composition.Its specific formula is shown in Table 2, and wherein each component content is in terms of parts by weight.
The pellet of extrusion is dried into 2h in 80 DEG C of constant temperature ovens, TVOC test is according to the meeting of German automobiles industrial combination
Standard VDA277 is tested.Specific performance the results are shown in Table 2.
Embodiment 20
By the Cellulose nanocrystal body (average BET specific surface area 150m2/ g, average length 150nm, mean breadth
12nm, average surface charge density 0.2e/nm2, China Forestry Science Research Institute, in its specific preparation method and embodiment 1~6
Only sulfuric acid/cellulose rate of charge is different in step 2 for the preparation method of Cellulose nanocrystal body, is 10mL/g, other steps with
The preparation method of Cellulose nanocrystal body is consistent in embodiment 1~6) and the fully sulfurized silicon rubber powder (trade mark VP-602, it is flat
Equal 0.2 μm of particle diameter, gel content 90wt%；Beijing Chemical Research Institute) it is sufficiently mixed and obtains the VOC inhibitor；It will obtain again
The VOC inhibitor and HOPP (K1712, Sinopec Beijing Yanshan Mountain branch company), acid-acceptor (zinc stearate, day
The prosperous Chemical Co., Ltd. in PORT OF JINSHI), (antioxidant 1076 belongs to Hinered phenols antioxidant, chemical entitled β-(3,5- bis- to antioxidant
Tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, and irgasfos 168, belong to phosphoric acid ester antioxidant, chemistry is entitled
The weight ratio of three (2,4- di-tert-butylphenol) phosphite esters, antioxidant 1076 and irgasfos 168 is 1:2, both come from German bar
Si Fu companies) it is put into homogenizer, stirred 3 minutes under 300 revs/min of rotating speed, each component is sufficiently mixed uniformly；With
Said mixture material is kneaded into unit (MKD-30, BUSS companies of Switzerland) by the BUSS in the range of 190 DEG C~220 DEG C afterwards,
Extruding pelletization under conditions of vacuum -0.08MPa is kept, low VOC polypropylene resin composites are obtained.Its specific formula is shown in Table 2,
Wherein each component content is in terms of parts by weight.
The pellet of extrusion is dried into 2h in 80 DEG C of constant temperature ovens, TVOC test is according to the meeting of German automobiles industrial combination
Standard VDA277 is tested.Specific performance the results are shown in Table 2.
Comparative example 5~8
By with the HOPP of the identical source of embodiment 11~20, fully sulfurized silicon rubber powder, Cellulose nanocrystal body,
The raw materials such as acid-acceptor (zinc stearate), adsorbent (RS378, German Dao Xu high polymer materials Co., Ltd), antioxidant are by table 2
Specific proportioning is weighed, and is respectively put into homogenizer, is stirred 3 minutes under 300 revs/min of rotating speed, each component is fully mixed
Close uniform.Said mixture material is then kneaded into unit by the BUSS in the range of 190 DEG C~220 DEG C, keep vacuum-
Extruding pelletization under conditions of 0.08MPa, obtains polypropene composition.Its specific formula is shown in Table 2, and wherein each component content is with weight
Measure number meter.
The pellet of extrusion is dried into 2h in 80 DEG C of constant temperature ovens, TVOC test is according to the meeting of German automobiles industrial combination
Standard VDA277 is tested.Specific performance the results are shown in Table 2.
The embodiment 11~20 of table 2, the component proportion of comparative example 5~8 and the performance test results
It was found from the data of Tables 1 and 2, by adding the method that VOC inhibitor compounds acid-acceptor, poly- third can be significantly reduced
The VOC content of ene compositions, can make the total volatile organism (TVOC) of polypropene composition be less than 50 μ gC/g.
Claims (16)
1. a kind of low VOC polypropylene resin composites, include the following components of blending：Polypropylene, VOC inhibitor；
Wherein, counted by 100 parts by weight of polypropylene, the VOC inhibitor is 0.1~10 parts by weight；
The VOC inhibitor includes following components：Fully sulfurized silicon rubber powder, Cellulose nanocrystal body；Wherein, pressed down with accounting for VOC
The percentage composition meter of total formulation weight, fully sulfurized silicon rubber powder is 0wt%~80wt%, and Cellulose nanocrystal body is 20wt%
~100wt%；
The rubber particles average grain diameter of the fully sulfurized silicon rubber powder is 0.05~1 μm, and it has cross-linked structure, gel content
For 60wt% or higher.
2. low VOC polypropylene resin composites according to claim 1, it is characterised in that：
The VOC inhibitor is 0.1~5 parts by weight.
3. low VOC polypropylene resin composites according to claim 1, it is characterised in that：
The Cellulose nanocrystal body surface density of surface charge is 0.1~0.4e/nm2；Length is 90~300nm；Width be 5~
15nm；BET specific surface area is 100~350m2/g。
4. low VOC polypropylene resin composites according to claim 1, it is characterised in that：
The polypropylene includes HOPP and acrylic resin copolymer.
5. low VOC polypropylene resin composites according to claim 1, it is characterised in that：
Include acid-acceptor；Counted by 100 parts by weight of polypropylene, the acid-acceptor is 0.05~1 parts by weight.
6. low VOC polypropylene resin composites according to claim 5, it is characterised in that：
The acid-acceptor is 0.1~0.6 parts by weight.
7. the low VOC polypropylene resin composites according to claim 5 or 6, it is characterised in that：
The acid-acceptor is in metal oxide, lactate, benzoate, silicate and stearate containing Na, Ca, Zn
It is at least one；The stearate containing Na, Ca, Zn is selected from least one of calcium stearate, zinc stearate, odium stearate.
8. low VOC polypropylene resin composites according to claim 7, it is characterised in that：
The metal oxide is selected from least one of calcium oxide, zinc oxide；The silicate is selected from natural or synthetic water
Talcum.
9. low VOC polypropylene resin composites according to claim 1, it is characterised in that：
Include antioxidant；Counted by 100 parts by weight of polypropylene, the consumption of the antioxidant is 0.1~0.5 parts by weight.
10. low VOC polypropylene resin composites according to claim 9, it is characterised in that：
The consumption of the antioxidant is 0.15~0.3 parts by weight.
11. the low VOC polypropylene resin composites according to claim 9 or 10, it is characterised in that：
The antioxidant is selected from the mixture of Hinered phenols antioxidant and phosphoric acid ester antioxidant；The Hinered phenols antioxidant and
The weight ratio of phosphoric acid ester antioxidant is 1:(1~4).
12. low VOC polypropylene resin composites according to claim 11, it is characterised in that：
The weight ratio of Hinered phenols antioxidant and the phosphoric acid ester antioxidant is 1：(1~3).
13. low VOC polypropylene resin composites according to claim 11, it is characterised in that：
The Hinered phenols antioxidant be selected from four [β-(3,5- di-tert-butyl-hydroxy phenyls) propionic acid] pentaerythritol esters, β-(3,
5- di-tert-butyl-hydroxy phenyls) the positive octadecanol ester of propionic acid, N, N'- is double-(3- (3,5- di-tert-butyl-hydroxy phenyls) third
Acyl group) hexamethylene diamine, at least one of 1,3,5- tri- (3,5- di-tert-butyl-4-hydroxyl benzyls) isocyanuric acid；The phosphate
Kind antioxidant is selected from three (2,4- di-tert-butylphenols) phosphite esters, double (2,4- DI-tert-butylphenol compounds) pentaerythritol diphosphites
At least one of.
14. the preparation method of the low VOC polypropylene resin composites according to one of claim 1~13, it is characterised in that：
Including will be well mixed comprising the component including the polypropylene, VOC inhibitor by the content, melt blending is made described
Low VOC polypropylene resin composites.
15. the preparation method of low VOC polypropylene resin composites according to claim 14, it is characterised in that：
The vacuum of device vacuum system is kept during the melt blending more than -0.05MPa.
16. the preparation method of low VOC polypropylene resin composites according to claim 15, it is characterised in that：
The vacuum of device vacuum system is kept during the melt blending more than -0.08MPa.
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| EP4182363A2 (en) | 2020-07-17 | 2023-05-24 | ExxonMobil Chemical Patents Inc. | Polymers with low levels of volatile organic compounds and methods of making such polymers |
| CN114573918A (en) * | 2022-04-18 | 2022-06-03 | 珠海瑞杰包装制品有限公司 | High-barrier low-odor polyolefin composition and preparation method thereof |
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