CN109294071A - Low VOC polypropylene resin composite and preparation method thereof - Google Patents
Low VOC polypropylene resin composite and preparation method thereof Download PDFInfo
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- CN109294071A CN109294071A CN201710608419.9A CN201710608419A CN109294071A CN 109294071 A CN109294071 A CN 109294071A CN 201710608419 A CN201710608419 A CN 201710608419A CN 109294071 A CN109294071 A CN 109294071A
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- 239000004743 Polypropylene Substances 0.000 title claims abstract description 97
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 97
- -1 polypropylene Polymers 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000000805 composite resin Substances 0.000 title abstract 5
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 42
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 40
- KBXJHRABGYYAFC-UHFFFAOYSA-N octaphenylsilsesquioxane Chemical compound O1[Si](O2)(C=3C=CC=CC=3)O[Si](O3)(C=4C=CC=CC=4)O[Si](O4)(C=5C=CC=CC=5)O[Si]1(C=1C=CC=CC=1)O[Si](O1)(C=5C=CC=CC=5)O[Si]2(C=2C=CC=CC=2)O[Si]3(C=2C=CC=CC=2)O[Si]41C1=CC=CC=C1 KBXJHRABGYYAFC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 26
- 239000002250 absorbent Substances 0.000 claims abstract description 12
- 230000002745 absorbent Effects 0.000 claims abstract description 12
- 239000012855 volatile organic compound Substances 0.000 claims description 68
- 239000011342 resin composition Substances 0.000 claims description 30
- 238000002156 mixing Methods 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 12
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 7
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 6
- 239000002516 radical scavenger Substances 0.000 claims description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000002401 inhibitory effect Effects 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 230000005764 inhibitory process Effects 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 claims description 3
- VNQNXQYZMPJLQX-UHFFFAOYSA-N 1,3,5-tris[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-1,3,5-triazinane-2,4,6-trione Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CN2C(N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C(=O)N(CC=3C=C(C(O)=C(C=3)C(C)(C)C)C(C)(C)C)C2=O)=O)=C1 VNQNXQYZMPJLQX-UHFFFAOYSA-N 0.000 claims description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-M Lactate Chemical compound CC(O)C([O-])=O JVTAAEKCZFNVCJ-UHFFFAOYSA-M 0.000 claims description 2
- BGHBLQKNCVRIKV-UHFFFAOYSA-N OP(O)OP(O)O.OCC(CO)(CO)CO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O Chemical compound OP(O)OP(O)O.OCC(CO)(CO)CO.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)O BGHBLQKNCVRIKV-UHFFFAOYSA-N 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims 1
- 239000004033 plastic Substances 0.000 abstract description 5
- 229920003023 plastic Polymers 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000012567 medical material Substances 0.000 abstract description 3
- 239000005022 packaging material Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 13
- 239000003463 adsorbent Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 238000012545 processing Methods 0.000 description 6
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 4
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- 235000013539 calcium stearate Nutrition 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000011701 zinc Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 239000005003 food packaging material Substances 0.000 description 2
- 239000004611 light stabiliser Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 101100070629 Arabidopsis thaliana HHP4 gene Proteins 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000009383 gan-kang Substances 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002091 nanocage Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920005606 polypropylene copolymer Polymers 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/549—Silicon-containing compounds containing silicon in a ring
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to plastic applications, a kind of low VOC polypropylene resin composite and preparation method thereof is provided.The low VOC polypropylene resin composite includes the following components being blended: polypropylene, octaphenyl silsesquioxane, acid absorbent and antioxidant；Relative to the polypropylene of 100 parts by weight, octaphenyl silsesquioxane is 0.05~1.8 parts by weight, and acid absorbent is 0.05~1 parts by weight, and antioxidant is 0.05~1 parts by weight.The TVOC of low VOC polypropylene resin composite of the invention is lower than 50 μ gC/g；And the preparation process of the low VOC polypropylene resin composite is simple and reliable, input cost is lower, can be widely applied to the fields such as the higher superior automobile inside gadget of environmental requirement, medical and packaging material for food.
Description
Technical Field
The invention relates to the field of plastics, in particular to a low-VOC polypropylene resin composition and a preparation method thereof.
Background
Polypropylene (PP) has been widely used in various fields of people's life because of its advantages of excellent comprehensive properties, wide sources, high quality and low cost. However, the existing polypropylene materials and products have the problems of environment pollution and harm to human health caused by release of Volatile Organic Compounds (VOC) to different degrees, which limits the application of the polypropylene materials in the fields of high-grade automotive upholsteries with higher environmental protection requirements, medical and food packaging materials and the like to a great extent. Therefore, research and development of the environment-friendly low-VOC polypropylene resin and the material can expand the application field of PP and meet the requirements of green environment-friendly materials.
At present, most of the reports on the research of low-VOC polypropylene materials adopt chemical reaction, physical adsorption and melt devolatilization technologies to improve the emission problem of VOC in the original polypropylene materials. For example, CN101570612A reduces VOC content by adding an inorganic photocatalyst to decompose organic small molecules, but the composition is complex and the effect is limited. CN101255252A lowered the VOC of the material by adding organic repellents (such as isopropyl alcohol/water), but this approach has compatibility and durability issues. EP1988122A1 adopts metallocene polypropylene resin as matrix resin to prepare low VOC automotive interior materials; EP 2154190a1 uses specific light stabilizers (such as light stabilizer 119) to prepare polypropylene composites with low VOC content; CN101691435A produced a low VOC polypropylene composite by producing a co-polypropylene using a specific hydrogen blending process. The invention only aims at improving a certain factor generating VOC and cannot solve the problem of VOC generated by various factors at the same time.
Physical adsorption can adsorb all small molecules produced by PP, and the addition of physical adsorbents is a common method. For example, CN1727389A and CN1727390A disclose the use of fine-pore silica gel and molecular sieves as adsorbents to reduce the odor of materials and the volatilization problem of organic compounds, and CN102276921A discloses the use of vegetable fibers as adsorbents to reduce the odor of polypropylene materials. Although the method adopting the adsorbent can play a certain role in reducing the polypropylene VOC, the problem of adsorption balance still exists, and the balance moves to the desorption direction at a higher temperature, so that the hidden danger of later-period re-release of the polypropylene VOC exists. In addition, the problems of the adsorption efficiency of the adsorbent, the compatibility with polypropylene, the dispersion of the adsorbent in the polypropylene matrix and the like still exist. Therefore, there is still a need to develop a new polypropylene resin composition having a low VOC content.
Disclosure of Invention
In order to solve the above technical problems of the prior art, the present invention is directed to provide a novel low VOC polypropylene resin composition and a method for preparing the same.
According to a first aspect of the present invention, the present invention provides a low VOC polypropylene resin composition comprising blended components of: polypropylene, octaphenyl silsesquioxane, an acid acceptor and an antioxidant; the octaphenyl silsesquioxane is 0.05-1.8 parts by weight, the acid acceptor is 0.05-1 part by weight, and the antioxidant is 0.05-1 part by weight, relative to 100 parts by weight of the polypropylene.
According to a second aspect of the present invention, the present invention provides a method for preparing the low VOC polypropylene resin composition, comprising: mixing the components including the polypropylene, octaphenyl silsesquioxane, an acid absorbent and an antioxidant, and then melt blending to obtain the low VOC polypropylene composition.
Aiming at the problems of high VOC content and the like in the existing polypropylene material, the invention selects the octaphenyl silsesquioxane with nanometer characteristics to effectively adsorb VOC in polypropylene, and fully exerts the good synergistic dispersion effect of the octaphenyl silsesquioxane on an antioxidant in the polypropylene, thereby greatly inhibiting VOC generated by degradation and further remarkably reducing the volatilization of VOC in the polypropylene. The Total Volatile Organic Compound (TVOC) content of the provided polypropylene resin composition is lower than 50 mu g.C/g; and the low VOC polypropylene resin composition has simple and reliable preparation process and low input cost, and can be widely applied to the fields of high-grade automotive upholsteries with higher environmental protection requirements, medical and food packaging materials and the like.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
According to a first aspect of the present invention, the present invention provides a low VOC polypropylene resin composition comprising blended components of: polypropylene, octaphenyl silsesquioxane, an acid acceptor and an antioxidant; 0.05 to 1.8 parts by weight of octaphenyl silsesquioxane relative to 100 parts by weight of the polypropylene; the acid absorbent is 0.05-1 part by weight, and the antioxidant is 0.05-1 part by weight.
In the present invention, the polypropylene includes various types of polypropylene resins disclosed in the prior art, including homo-polypropylene and co-polypropylene resins, and the like.
According to the invention, the octaphenyl silsesquioxane, the acid absorbent and the antioxidant are compounded, so that the dispersion effect of the acid absorbent and the antioxidant in the polypropylene resin can be effectively improved, the action efficiency of the antioxidant and the acid absorbent is improved, and the total VOC in the polypropylene is remarkably reduced. Wherein,
the octaphenyl silsesquioxane has the following cage structure:
the octaphenyl silsesquioxane (also called as octaphenyl cage silsesquioxane) has higher thermal stability, and the inventor finds that the compound does not additionally generate VOC in the processing, using and storing processes, the eight tops of the cage structure of the octaphenyl silsesquioxane have nonpolar benzene rings and polypropylene which have better compatibility, and the nano cage structure can effectively adsorb micromolecular hydrocarbon VOC; and the octaphenyl silsesquioxane can be dispersed in the polypropylene matrix in a nanometer mode, so that the emission of VOC in the polypropylene can be effectively inhibited or slowed down, and the total amount of VOC in the polypropylene is reduced.
Said octaphenylsilsesquioxanes are commercially available and, due to the limitations of the existing preparation methods, tend to contain other impurities, preferably selected from N2Octaphenyl silsesquioxane with a thermal degradation temperature (5 wt% weight loss) above 440 ℃ under atmospheric conditions, such as octaphenyl silsesquioxane MS0840 from hybrid plastics, USA.
The octaphenylsilsesquioxane is preferably 0.2 to 0.9 part by weight, more preferably 0.5 to 0.8 part by weight, based on 100 parts by weight of the polypropylene.
In order to achieve the effect of improving the VOC (volatile organic compound) inhibition effect, the low-VOC polypropylene resin composition also comprises an antioxidant, and the antioxidant and the octaphenyl silsesquioxane have a good synergistic dispersion effect and can effectively reduce the VOC content in the polypropylene. The antioxidant is preferably 0.1 to 0.8 part by weight, more preferably 0.3 to 0.6 part by weight, based on 100 parts by weight of the polypropylene. In addition, the antioxidant can be selected from various antioxidants commonly used in polypropylene in the prior art.
In one embodiment, the hindered phenolic antioxidant is preferably selected from at least one of pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] (antioxidant 1010), N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate (antioxidant 1076), N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine (antioxidant 1098), and 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid (antioxidant 3114).
The phosphate antioxidant is preferably selected from tris (2, 4-di-tert-butylphenol) phosphite (antioxidant 168) and/or bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite (antioxidant 626).
Preferably, the antioxidant is a mixture of a hindered phenol antioxidant and a phosphate antioxidant, and the weight ratio of the hindered phenol antioxidant to the phosphate antioxidant is 1: 1-8, preferably 1: 1-6, and more preferably 1: 1-4.
In the low-VOC polypropylene resin composition, the acid absorbent can react with diluted acid catalyst residues possibly existing in polypropylene, so that the effect of reducing or inhibiting VOC generated by the degradation of the polypropylene catalyzed by the diluted acid is achieved. The acid acceptor has the main property of alkalinity, can react with acid catalyst residues to play a role in neutralization, and the acid acceptor required by the invention can be well dispersed in polypropylene. The acid scavenger may be selected from at least one of metal oxide, lactate, benzoate, silicate and Na, Ca or Zn-containing stearate, preferably Na, Ca or Zn-containing stearate. Wherein the metal oxide is preferably selected from calcium oxide and/or zinc oxide; the silicate may be selected from natural or synthetic hydrotalcite; the Na, Ca or Zn-containing stearate is preferably at least one selected from the group consisting of calcium stearate, zinc stearate and sodium stearate.
The acid scavenger is preferably 0.1 to 0.8 parts by weight, more preferably 0.2 to 0.5 parts by weight, based on 100 parts by weight of the polypropylene.
In addition, in the low VOC polypropylene resin composition of the present invention, a common processing aid may be added according to the specific processing requirements, for example: the dosage of the lubricant, the antistatic agent, the dispersant, the pigment and the like is conventional dosage or is adjusted according to the requirement of actual situation.
According to a second aspect of the present invention, the present invention provides a method for preparing the low VOC polypropylene resin composition, comprising: mixing the components including the polypropylene, the octaphenyl silsesquioxane, the acid absorbent and the antioxidant, and then carrying out melt blending to obtain the low-VOC polypropylene resin composition.
According to a particular embodiment, the preparation method comprises the following steps:
(1) uniformly mixing the octaphenyl silsesquioxane, the antioxidant and the acid absorbent, preferably dry-mixing for 1-2 minutes to obtain a VOC (volatile organic compound) inhibition mixture;
(2) uniformly mixing the VOC inhibiting mixture and the dried polypropylene according to the required content, preferably dry-mixing for 3-5 minutes to obtain a premix;
(3) and melt blending the premix to obtain the low VOC polypropylene resin composition.
For better VOC removal, the vacuum degree of a vacuum system of equipment is preferably kept above-0.05 MPa, more preferably above-0.08 MPa during the melt blending.
In addition, during the processing, after melt blending, various molding processes may be performed to make the low VOC polypropylene resin composition in a granular form (e.g., by extrusion granulation), a plate, etc., according to the needs of practical applications.
In the preparation method, the material melt blending temperature is the blending temperature used in the common polypropylene processing, and is selected within the range of ensuring that the matrix resin is completely melted and cannot be decomposed, generally 180-220 ℃, and the preferred processing temperature is 190-220 ℃; the screw rotating speed of the melt blending equipment is 300-450 rpm.
In the preparation method of the present invention, the mixing equipment for each material can adopt various mixing equipment used in the prior art, such as a stirrer, a kneader and the like; the used melt blending equipment is general blending equipment in the rubber and plastic processing industry, and can be a double-screw extruder, a BUSS mixing unit and the like.
The following examples are given by way of illustration only, and the scope of the present invention is not limited to these examples.
In the following examples and comparative examples, antioxidant 1010 and antioxidant 168 were obtained from basf, germany; octaphenyl silsesquioxane was MS0840 available from hybrid plastic, USA, and acid scavenger was calcium stearate available from Gankang chemical Co., Ltd, Tianjin City. The BUSS mixing unit has the model of MKD-30 and is produced by the Swiss BUSS company.
Examples 1 to 10
Examples 1 to 10 are provided to illustrate the low VOC polypropylene resin composition of the present invention and the method for preparing the same.
Putting octaphenyl silsesquioxane, calcium stearate, an antioxidant 1010 and an antioxidant 168 (the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1: 4) into a high-speed stirrer, and stirring at the rotating speed of 300 revolutions per minute for 2 minutes to fully and uniformly mix the components to obtain a VOC (volatile organic compound) inhibition mixture; and stirring the obtained VOC inhibiting mixture and copolymerized polypropylene (HHP4, China petrochemical metallocene company) at 300 r/min for 3 minutes, then extruding and granulating the obtained premix through a BUSS mixing unit at the temperature of 190-220 ℃ under the condition of keeping the vacuum degree of-0.08 MPa to obtain the low-VOC polypropylene resin composition. The specific formula is shown in table 1, wherein the contents of all components are calculated by weight parts.
The extruded pellets were dried in a constant temperature oven at 80 ℃ for 2h and tested for TVOC according to the standard VDA277 of the German Association for the automotive industry. Specific performance results are shown in table 1.
Comparative examples 1 to 4
The raw materials of the polypropylene copolymer, calcium stearate, antioxidant and adsorbent (RS378, used in comparative example 4, Asahi Polymer materials Co., Ltd., DE.) from the same sources as in examples 1 to 10 were weighed in the specific proportions shown in Table 1, and each was stirred in a high-speed stirrer at a rotation speed of 300 rpm for 3 minutes to sufficiently and uniformly mix the components. And then, the premix is extruded and granulated by a BUSS mixing unit at the temperature of between 190 and 220 ℃ under the condition of keeping the vacuum degree of-0.08 MPa to obtain the polypropylene resin composition. The specific formula is shown in table 1, wherein the contents of all components are calculated by weight parts.
The extruded pellets were dried in a constant temperature oven at 80 ℃ for 2h and tested for TVOC according to the standard VDA277 of the German Association for the automotive industry. Specific performance results are shown in table 1.
Comparative examples 5 to 6
Polypropylene resin compositions were prepared according to the methods of examples 1 to 10, except that the amounts of octaphenylsilsesquioxane were adjusted to 3 parts by weight and 11 parts by weight, respectively, to obtain the polypropylene resin compositions. The specific formulation and performance results are shown in table 1.
TABLE 1 component proportions and Performance test results
As can be seen from the data in Table 1, the VOC content of the polypropylene composition can be significantly reduced by adding a certain amount of octaphenyl silsesquioxane to the polypropylene to compound an acid scavenger and an antioxidant, so that the Total Volatile Organic Compounds (TVOC) of the obtained polypropylene composition is lower than 50 [ mu ] g.C/g.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention. In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. A low VOC polypropylene resin composition characterized in that it comprises the following components blended together: polypropylene, octaphenyl silsesquioxane, an acid acceptor and an antioxidant; the octaphenyl silsesquioxane is 0.05-1.8 parts by weight, the acid acceptor is 0.05-1 part by weight, and the antioxidant is 0.05-1 part by weight, relative to 100 parts by weight of the polypropylene.
2. The low VOC polypropylene resin composition according to claim 1, wherein said octaphenyl silsesquioxane is in the range of 0.2 to 0.9 parts by weight, preferably 0.5 to 0.8 parts by weight, relative to 100 parts by weight of said polypropylene.
3. The low VOC polypropylene resin composition of claim 1 wherein said antioxidant is selected from hindered phenolic antioxidants and/or phosphate antioxidants;
the hindered phenol antioxidant is selected from at least one of pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine and 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid;
the phosphate antioxidant is selected from tris (2, 4-di-tert-butylphenol) phosphite and/or bis (2, 4-di-tert-butylphenol) pentaerythritol diphosphite.
4. The low-VOC polypropylene resin composition according to claim 3, wherein the antioxidant is a mixture of hindered phenol antioxidant and phosphate antioxidant, and the weight ratio of the hindered phenol antioxidant to the phosphate antioxidant is 1: 1-8.
5. The low VOC polypropylene resin composition according to any of claims 1 to 4, wherein said antioxidant is 0.1 to 0.8 parts by weight, preferably 0.3 to 0.6 parts by weight, based on 100 parts by weight of said polypropylene.
6. The low VOC polypropylene resin composition of claim 1 wherein said acid scavenger is selected from at least one of a metal oxide, lactate, benzoate, silicate and Na, Ca or Zn containing stearate.
7. The low VOC polypropylene resin composition according to any one of claims 1 to 6, wherein said acid scavenger is 0.1 to 0.8 parts by weight, preferably 0.2 to 0.5 parts by weight, relative to 100 parts by weight of said polypropylene.
8. The method for preparing the low VOC polypropylene resin composition of any one of claims 1-7, wherein the method comprises: mixing the components including the polypropylene, octaphenyl silsesquioxane, an acid absorbent and an antioxidant, and then melt blending to obtain the low VOC polypropylene composition.
9. The production method according to claim 8, wherein the production method comprises the steps of:
(1) uniformly mixing the octaphenyl silsesquioxane, the acid absorbent and the antioxidant to obtain a VOC (volatile organic compound) inhibition mixture;
(2) uniformly mixing the VOC-inhibiting mixture and the polypropylene to obtain a premix;
(3) and carrying out melt blending on the premix to obtain the low-VOC polypropylene resin composition.
10. The production method according to claim 8 or 9, wherein a vacuum degree of a vacuum system of a device is maintained at-0.05 MPa or more in the melt blending.
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