CN114835984A - Extinction polyvinyl chloride resin composition and hard plastic product prepared from same - Google Patents
Extinction polyvinyl chloride resin composition and hard plastic product prepared from same Download PDFInfo
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- CN114835984A CN114835984A CN202210572106.3A CN202210572106A CN114835984A CN 114835984 A CN114835984 A CN 114835984A CN 202210572106 A CN202210572106 A CN 202210572106A CN 114835984 A CN114835984 A CN 114835984A
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- polyvinyl chloride
- weight
- chloride resin
- resin composition
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 74
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 74
- 239000011342 resin composition Substances 0.000 title claims abstract description 42
- 230000008033 biological extinction Effects 0.000 title claims abstract description 20
- 229920003023 plastic Polymers 0.000 title claims abstract description 18
- 239000004033 plastic Substances 0.000 title claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 57
- -1 polypropylene Polymers 0.000 claims abstract description 41
- 239000004743 Polypropylene Substances 0.000 claims abstract description 34
- 229920001155 polypropylene Polymers 0.000 claims abstract description 34
- 239000004014 plasticizer Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 5
- 229920000578 graft copolymer Polymers 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- 125000005907 alkyl ester group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 11
- 239000000314 lubricant Substances 0.000 description 10
- 239000003963 antioxidant agent Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- 230000003078 antioxidant effect Effects 0.000 description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 6
- 239000012760 heat stabilizer Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 235000021355 Stearic acid Nutrition 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000008117 stearic acid Substances 0.000 description 5
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000001993 wax Substances 0.000 description 4
- 102220613496 Creatine kinase M-type_K10S_mutation Human genes 0.000 description 3
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 3
- OIDQOTHCTOVWOF-UHFFFAOYSA-N bis(6-methylheptyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCOC(=O)C1CCCCC1C(=O)OCCCCCC(C)C OIDQOTHCTOVWOF-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000004209 oxidized polyethylene wax Substances 0.000 description 3
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 description 2
- XTJFFFGAUHQWII-UHFFFAOYSA-N Dibutyl adipate Chemical compound CCCCOC(=O)CCCCC(=O)OCCCC XTJFFFGAUHQWII-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- IZRBAWXNLPBYKE-UHFFFAOYSA-N cyclohexane dioctyl benzene-1,2-dicarboxylate Chemical group C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1CCCCC1 IZRBAWXNLPBYKE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- MGWAVDBGNNKXQV-UHFFFAOYSA-N diisobutyl phthalate Chemical compound CC(C)COC(=O)C1=CC=CC=C1C(=O)OCC(C)C MGWAVDBGNNKXQV-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 150000004665 fatty acids Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000012780 transparent material Substances 0.000 description 2
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 description 1
- ALKCLFLTXBBMMP-UHFFFAOYSA-N 3,7-dimethylocta-1,6-dien-3-yl hexanoate Chemical compound CCCCCC(=O)OC(C)(C=C)CCC=C(C)C ALKCLFLTXBBMMP-UHFFFAOYSA-N 0.000 description 1
- SIXWIUJQBBANGK-UHFFFAOYSA-N 4-(4-fluorophenyl)-1h-pyrazol-5-amine Chemical compound N1N=CC(C=2C=CC(F)=CC=2)=C1N SIXWIUJQBBANGK-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- ZVFDTKUVRCTHQE-UHFFFAOYSA-N Diisodecyl phthalate Chemical compound CC(C)CCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC(C)C ZVFDTKUVRCTHQE-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- MTUBBMSQXXJFQP-UHFFFAOYSA-N OC(CCCCCCCCCCCCCCCCC(=O)OCC(O)CO)(O)O Chemical compound OC(CCCCCCCCCCCCCCCCC(=O)OCC(O)CO)(O)O MTUBBMSQXXJFQP-UHFFFAOYSA-N 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- ZWYAVGUHWPLBGT-UHFFFAOYSA-N bis(6-methylheptyl) decanedioate Chemical compound CC(C)CCCCCOC(=O)CCCCCCCCC(=O)OCCCCCC(C)C ZWYAVGUHWPLBGT-UHFFFAOYSA-N 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- HBGGXOJOCNVPFY-UHFFFAOYSA-N diisononyl phthalate Chemical compound CC(C)CCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCC(C)C HBGGXOJOCNVPFY-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- XWVQUJDBOICHGH-UHFFFAOYSA-N dioctyl nonanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCC(=O)OCCCCCCCC XWVQUJDBOICHGH-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940127554 medical product Drugs 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- GVYLCNUFSHDAAW-UHFFFAOYSA-N mirex Chemical compound ClC12C(Cl)(Cl)C3(Cl)C4(Cl)C1(Cl)C1(Cl)C2(Cl)C3(Cl)C4(Cl)C1(Cl)Cl GVYLCNUFSHDAAW-UHFFFAOYSA-N 0.000 description 1
- RKISUIUJZGSLEV-UHFFFAOYSA-N n-[2-(octadecanoylamino)ethyl]octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(=O)NCCNC(=O)CCCCCCCCCCCCCCCCC RKISUIUJZGSLEV-UHFFFAOYSA-N 0.000 description 1
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 description 1
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 125000005498 phthalate group Chemical class 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003017 thermal stabilizer Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
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
A delustering polyvinyl chloride resin composition and a hard plastic product prepared from the delustering polyvinyl chloride resin composition are disclosed. The composition comprises extinction polyvinyl chloride resin, 3-5 parts by weight of chlorinated polypropylene, 1-5 parts by weight of plasticizer and 2-4 parts by weight of processing aid, based on 100 parts by weight of the extinction polyvinyl chloride resin; the gel content of the extinction polyvinyl chloride is 18-30 wt%; the chlorinated polypropylene is a (methyl) acrylate-chlorinated polypropylene graft copolymer with a grafting rate of 8-10 wt%.
Description
Technical Field
The invention relates to a delustering polyvinyl chloride resin composition. Rigid plastic articles made using the compositions of the present invention have improved low bleed and impact properties.
Background
Polyvinyl chloride resin (PVC) is one of five general-purpose resins. The composite material has the advantages of high physical performance, good processing performance, corrosion resistance, low price and the like, and is a main material for manufacturing hard plastic products, such as automobile control consoles, automobile interior parts, medical instrument shells, electronic product shells, outdoor sports equipment and the like.
Common rigid plastic products usually use common polyvinyl chloride resin as a base material, and a small amount of liquid plasticizer is added in order to improve flowability in the actual processing of finished products. However, these plasticizers also have a problem of surface precipitation while enhancing the plasticization of the resin. Causing the surface of the article to stick and ultimately affecting quality and appearance.
"preparation of medical matting PVC material" by dawn et al (plastics industry, vol 40, fourth, 4 p 2012) describes a medical PVC material in which matting PVC resin is blended with general PVC resin to reduce the precipitation of plasticizer. It is mentioned that matting materials generally mean articles having a surface gloss of from 2 to 15%, typically measured at an angle of 60 degrees. The delustered PVC resin contains a certain gel component, and shows viscoelasticity different from that of common resin in the processing process due to the action of gel, so that fine concave-convex fluctuation is formed on the surface of a product. Due to the existence of the gel structure, the precipitation of the plasticizer is hindered, the surface of the product is not sticky, the product has good hand feeling, and the soft product with the property similar to that of the thermoplastic elastomer is obtained. The purpose of adding ordinary PVC resin to the matt PVC resin is to improve the processability of the matt PVC resin and to reduce the cost.
CN113683847A discloses a keyboard cap, which is prepared by adjusting the formulation and preparation method of a delustred polyvinyl chloride resin composition, effectively improving the plasticization of the delustred polyvinyl chloride resin blend by adding chlorinated polypropylene and adjusting stabilizer and lubricant, improving the fluidity, and greatly increasing the glossiness, so that the processability and impact resistance of the delustred polyvinyl chloride resin can be greatly improved. The chlorinated polypropylene employed in this document is a conventional chlorinated polypropylene, which in one example is prepared by aqueous suspension, having a molecular weight of between 4000-20000, preferably between 5000-18000, more preferably between 6000-16000; the chlorine content is 20 to 40% by weight, preferably 22 to 38% by weight, more preferably 25 to 35% by weight.
Lesheng et al, "research on extinction properties of extinction PVC resin containing gel extinction" ("chemical production and technology", volume 10, No. 4, 2003) mentioned that, in terms of extinction properties, the extinction properties of extinction resins are continuously enhanced with the increase of gel content, the glossiness is only 1/4 of common PVC resins, and when the gel content reaches 10%, the influence of the increase of gel content on extinction properties is smaller and smaller.
Although the use of matte pvc helps prevent plasticizer bleed out and the addition of chlorinated polypropylene helps improve processability, existing matte pvc compositions do not meet the requirements for certain applications where impact resistance is a particular requirement, such as automotive instrument panels, portable medical device housings, electronics housings, outdoor sports equipment, and the like.
Accordingly, there remains a need in the art to develop a matte resin composition for rigid plastic articles having improved impact properties in addition to matte properties, low plasticizer extraction.
There is also a need in the art to develop rigid plastic articles made from the matte resin compositions.
Disclosure of Invention
It is an object of the present invention to provide a matting resin composition for rigid plastic articles having improved impact resistance in addition to matting properties, low plasticizer extraction properties.
Another object of the present invention is to provide a hard plastic article produced from the matte resin composition.
It is still another object of the present invention to provide use of the related resin composition in forming automotive parts (e.g., automobile instrument desk, automobile hard interior material, etc.), portable medical device housings, electronic product housings, outdoor sports equipment.
Accordingly, one aspect of the present invention relates to a matted polyvinyl chloride resin composition comprising a matted polyvinyl chloride resin, and 3 to 5 parts by weight of a chlorinated polypropylene, 1 to 5 parts by weight of a plasticizer and 2 to 4 parts by weight of a processing aid, based on 100 parts by weight of said matted polyvinyl chloride resin;
the gel content of the extinction polyvinyl chloride is 18-30 wt%;
the chlorinated polypropylene is a (methyl) acrylate-chlorinated polypropylene graft copolymer with a grafting rate of 8-10 wt%.
Another aspect of the present invention relates to a rigid plastic article obtained from the above-mentioned matte polyvinyl chloride resin composition, which has an Izod impact strength of 19KJ/m 2 Or higher.
Still another aspect of the invention relates to the use of the delustered polyvinyl chloride resin combination to form an automobile instrument desk, an automobile hard interior material, a portable medical device shell, an electronic product shell and outdoor sports equipment.
Detailed Description
The resin composition of the present invention comprises a matte polyvinyl chloride resin. In one embodiment of the present invention, the polymerization degree of the delustered polyvinyl chloride resin is between 800-1200, preferably between 850-1150, and more preferably between 900-1100.
The gel content of the matte polyvinyl chloride resin suitable for the resin composition of the present invention is 18 to 30% by weight, preferably 20 to 29% by weight, more preferably 22 to 28% by weight. The inventors of the present invention have found, through studies, that although it is known that a gel content of around 10% is already sufficient to prevent the plasticizer from bleeding out and to form a mat appearance, the impact strength of the final rigid plastic article can be further improved if the gel content is controlled to 18 to 30%.
The matte polyvinyl chloride resin suitable for the matte resin composition of the present invention is commercially available from japan koilou corporation under the trade name of K10 s.
The resin composition of the present invention further comprises 3 to 5 parts by weight, preferably 3.2 to 4.8 parts by weight, more preferably 3.5 to 4.5 parts by weight, of chlorinated polypropylene per 100 parts by weight of the above-mentioned matte polyvinyl chloride resin.
Chlorinated polypropylene suitable for use in the resin composition of the present invention is a chlorinated polypropylene grafted with a (meth) acrylic acid ester, non-limiting examples of suitable (meth) acrylic acid esters being, for example, C (meth) acrylic acid 1-6 Alkyl esters, such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, or mixtures of two or more thereof.
In the present invention, the term "(meth) acrylate" refers to acrylate, methacrylate, or a mixture of both in any ratio.
The molecular weight of the grafted chlorinated polypropylene is 5000-; the chlorine content is 20 to 40% by weight, preferably 22 to 38% by weight, more preferably 25 to 35% by weight.
The graft ratio of the grafted chlorinated polypropylene of the present invention is 8 to 10% by weight, preferably 8.2 to 9.8% by weight, more preferably 8.5 to 9.5% by weight.
The method for grafting the chlorinated polypropylene is not particularly limited, and may be a conventional grafting method known in the art. In one embodiment of the invention, the grafting method comprises heating chlorinated polypropylene and (meth) acrylate in solution at 90-110 ℃ and stirring for 2-4 hours.
The resin composition of the present invention further comprises 1 to 5 parts by weight, preferably 1.5 to 4.5 parts by weight, more preferably 2 to 4 parts by weight of a plasticizer. The plasticizer to be used is not particularly limited and may be a conventional plasticizer known in the art. In a preferred embodiment of the invention, non-limiting examples of suitable plasticizers are, for example, phthalates, fatty acid esters, phosphates or mixtures of two or more thereof.
Non-limiting examples of suitable phthalate-based plasticizers are, for example, dioctyl phthalate, diisooctyl phthalate, diisodecyl phthalate, diisononyl phthalate, dibutyl phthalate, diisobutyl phthalate, butylbenzyl phthalate, dimethyl phthalate, diethyl phthalate or mixtures of two or more thereof.
Non-limiting examples of suitable fatty acid ester plasticizers are, for example, dioctyl adipate, diisodecyl adipate, dioctyl azelate, dibutyl sebacate, dioctyl sebacate, diisooctyl di (2-ethylbutyrate) triethylene glycol ester, diisooctyl cyclohexane 1, 2-Dicarboxylate (DEHCH) or mixtures of two or more thereof.
Non-limiting examples of suitable phosphate plasticizers are, for example, triphenyl phosphate and tricresyl phosphate.
In one embodiment of the invention, the plasticizer is selected from di (2-ethylhexyl) sebacate (DOS, or diisooctyl sebacate), dioctyl adipate (DOA), dibutyl sebacate (DBS), di-n-butyl adipate (DBA), dibutyl phthalate (DBP), diisooctyl cyclohexane 1, 2-Dicarboxylate (DEHCH), or a mixture of two or more thereof.
In a preferred embodiment of the present invention, the plasticizer is diisooctyl cyclohexane 1, 2-Dicarboxylate (DEHCH) available from hanhua group.
The resin composition of the present invention further comprises 2 to 4 parts by weight, preferably 2.5 to 3.5 parts by weight of a processing aid, and the processing aid suitable for the resin composition of the present invention is not particularly limited and may be a conventional processing aid known in the art, for example, the processing aid may be an ACR type processing aid such as ACR-201 (Weifang double source aid) which is specialized for transparency.
The resin composition of the present invention may optionally further comprise 1 to 2 parts by weight of a lubricant. The lubricant to be used is not particularly limited and may be a conventional lubricant known in the art.
Non-limiting examples of suitable lubricants are, for example, fatty acids (e.g., stearic acid), fatty acid amides (e.g., stearamide, N, ethylene bis stearamide, oleamide, butyl stearate, glycerol trihydroxystearate), hydrocarbons (e.g., microcrystalline paraffin, paraffin wax, polyethylene wax, oxidized polyethylene wax, Fischer-Tropsch wax) or mixtures of two or more thereof in any ratio.
The resin composition of the present invention may optionally further comprise other conventional additives such as heat stabilizers, light stabilizers, antioxidants, fillers and the like.
In one embodiment of the present invention, the thermal stabilizer comprises an organotin stabilizer, which may be a commercially available product such as the TM181 stabilizer from Rohm and Haas, U.S.A.
In one embodiment of the present invention, the antioxidant comprises bisphenol a antioxidant, which may be a commercially available product.
In one example of the invention, the processing aid comprises an ACR-type processing aid, such as ACR-201 (a mirex dual-source aid) specific to a transparency.
In one embodiment of the present invention, the resin composition of the present invention comprises:
the resin composition of the present invention can be prepared by the following method:
(1) mixing delustered polyvinyl chloride resin, a heat stabilizer, a lubricant, a processing aid and chlorinated polypropylene in a mixer, heating to 60 ℃, adding a plasticizer, heating to 115-120 ℃, cooling to below 45 ℃, uniformly mixing, and discharging to obtain a mixture;
(2) and (3) extruding and granulating the mixture to obtain the granular material containing the extinction polyvinyl chloride resin for preparing the medical hard product. The processing temperature is 150-170 ℃.
The resin composition pellets of the present invention can be processed to produce various hard plastic articles having high impact resistance, which have a matte surface and little bleed-out of plasticizer. Non-limiting examples of such rigid plastic articles are, for example, automotive parts (e.g., automotive instrument panels, automotive hard trim materials, etc.), portable medical device housings, electronic product housings, outdoor sports equipment, and the like. If desired, the resin composition of the present invention can also be processed into various parts requiring high impact resistance, such as automobile handlebars, automobile bumpers and the like.
Examples
The present invention will be further described with reference to specific examples, but the following examples are only preferred embodiments of the present invention, and are not intended to be exhaustive.
Example 1
The formula is as follows: (weight)
The matte polyvinyl chloride resin had a gel content of 20 wt% and a polymerization degree of 1030, and was obtained from K10S matte resin available from Brillouin, Japan.
The heat stabilizer selected was Rohm and Haas TM-181 organotin stabilizer.
The lubricant is a mixture of stearic acid and oxidized polyethylene wax. Wherein, the usage amount of stearic acid is 1.5 parts, SA1801 of Indonesian and oxidized polyethylene wax are 1 part, and AC-629 of HONEYWELL are adopted.
The antioxidant is bisphenol A antioxidant and adopts a product provided by China petrochemical three-well chemistry.
The processing aid is an ACR type processing aid, adopts a Weifang double-source aid and is specially used for ACR-201 of the transparent material.
The chlorinated polypropylene is a product obtained by grafting chlorinated polypropylene and methyl acrylate, and has the grafting rate of about 9 wt%, the molecular weight of 15000 and the chlorine content of 30%.
The plasticizer is cyclohexane 1, 2-dioctyl phthalate (DEHCH) produced in Korea.
(1) Mixing delustered polyvinyl chloride resin, a heat stabilizer, a lubricant, a processing aid and chlorinated polypropylene in a mixer, heating to 60 ℃, adding a plasticizer, heating to about 180 ℃, cooling to below 45 ℃, uniformly mixing, and discharging to obtain a mixture;
(2) and (3) extruding and granulating the mixture to obtain the granular material containing the extinction polyvinyl chloride resin for preparing the hard plastic product. The processing temperature was about 160 ℃. The extruder model is a small conical twin-screw extruder SJZ20/40 Hongyuan, the screw rotating speed is about 40rpm, and the granular material of the extinction polyvinyl chloride resin is obtained.
Example 2
The formula is as follows: (weight)
The matte polyvinyl chloride resin had a gel content of about 20% by weight and a degree of polymerization 1030, and was obtained from K10S matte resin available from Korea.
The heat stabilizer selected was Rohm and Haas TM-181 organotin stabilizer.
The lubricant is a mixture of stearic acid and polyethylene wax. Wherein, the usage amount of stearic acid is 0.5 part, SA1801 of Innesvin is adopted, the usage amount of polyethylene wax is 1 part, and AC-6A of United states Honeywell is adopted.
The antioxidant is bisphenol A antioxidant and adopts a product provided by China petrochemical three-well chemistry.
The processing aid is an ACR type processing aid, adopts a Weifang double-source aid and is specially used for ACR-201 of the transparent material.
The chlorinated polypropylene is a product obtained by grafting the chlorinated polypropylene and ethyl acrylate, and has the grafting rate of about 9%, the molecular weight of 15000 and the chlorine content of 30%.
The plasticizer is cyclohexane 1, 2-dioctyl phthalate (DEHCH) produced in Korea.
(1) Mixing delustered polyvinyl chloride resin, a heat stabilizer, a lubricant, a processing aid and chlorinated polypropylene in a mixer, heating to 60 ℃, adding a plasticizer, heating to 118 ℃, cooling to below 45 ℃, uniformly mixing, and discharging to obtain a mixture;
(2) and (3) extruding and granulating the mixture to obtain the granular material containing the extinction polyvinyl chloride resin for preparing the hard plastic product. The processing temperature is about 160 ℃. The extruder model is a small conical twin-screw extruder SJZ20/40 Hongyuan, the screw rotating speed is about 40rpm, and the granular material of the extinction polyvinyl chloride resin is obtained.
Comparative example 1
Comparative example 1 was similar to example 1 except that the matte polyvinyl chloride resin was replaced with an equal amount of the ordinary polyvinyl chloride resin and the degree of polymerization was 1000.
Comparative example 2
Comparative example 2 in comparison with example 1, the extinction polyvinyl chloride resin was replaced with a general polyvinyl chloride resin having a polymerization degree of 1000, and the modified chlorinated polypropylene was replaced with a general chlorinated polypropylene having a chlorine content of 30% and a trade name of DX530P from toyobo japan.
Comparative example 3
Comparative example 3 compared to example 1, the modified chlorinated polypropylene was changed to ordinary chlorinated polypropylene still using the matte polyvinyl chloride resin, with a chlorine content of 30%. Under the designation DX530P from eastern japan.
Comparative example 4
Comparative example 4 the matte polyvinyl chloride resin having a gel content of 20% was changed to a matte polyvinyl chloride resin having a gel content of 40% (K10M resin available from japanese koyun chemical) in comparison with example 1, and the balance was not changed.
Comparative example 5
Comparative example 5 compared with example 1, 100 parts of a matte polyvinyl chloride resin having a gel content of 20% was changed to 50 parts of ordinary polyvinyl chloride and 50 parts of a matte polyvinyl chloride resin having a gel content of 20% (available from K10S resin of Korea chemical Co., Ltd.), with the remainder being unchanged.
The properties of the above resins were tested according to GB/T11593-2020 and the results are shown in the following table.
Examples 1 and 2 using the composition were compared with comparative examples. The specific test method can be referred to the standard, and the results are as follows.
The experimental results show that the delustered polyvinyl chloride with specific gel content in the resin composition is combined with the grafted chlorinated polypropylene, so that the impact strength of a hard product prepared from the resin composition can be obviously improved, and compared with a product prepared from the common polyvinyl chloride resin and the delustered polyvinyl chloride, all other indexes are not obviously changed, the surface has an obvious matte effect, and the surface precipitation of the product can be effectively prevented. Therefore, the resin composition of the present invention is very suitable for the preparation of automobile parts (e.g., automobile instrument desk, automobile hard interior material, etc.), portable medical device housings, electronic product housings, outdoor sports equipment, etc., and also for the manufacture of medical products which come into contact with a medicament, such as disposable syringes, etc.
Claims (10)
1. A delustered polyvinyl chloride resin composition comprises a delustered polyvinyl chloride resin, 3-5 parts by weight of chlorinated polypropylene, 1-5 parts by weight of a plasticizer and 2-4 parts by weight of a processing aid based on 100 parts by weight of the delustered polyvinyl chloride resin;
the gel content of the extinction polyvinyl chloride is 18-30 wt%;
the chlorinated polypropylene is a (methyl) acrylate-chlorinated polypropylene graft copolymer with a grafting rate of 8-10 wt%.
2. The delustered polyvinyl chloride resin composition as claimed in claim 1, wherein the polymerization degree of said delustered polyvinyl chloride resin is between 800-1200, preferably between 850-1150, more preferably between 900-1100.
3. A matted polyvinyl chloride resin composition according to claim 1 wherein said matted polyvinyl chloride resin has a gel content of from 20 to 29% by weight, more preferably from 22 to 28% by weight.
4. The matted polyvinyl chloride resin composition according to claim 1, wherein said resin composition comprises 3.2 to 4.8 parts by weight, more preferably 3.5 to 4.5 parts by weight, based on 100 parts by weight of said matted polyvinyl chloride resin, of chlorinated polypropylene having a molecular weight of 5000-; the chlorine content is 20 to 40% by weight, preferably 22 to 38% by weight, more preferably 25 to 35% by weight.
5. A matted polyvinyl chloride resin composition according to claim 1, wherein said chlorinated polypropylene has a graft ratio of 8.2 to 9.8% by weight, more preferably 8.5 to 9.5% by weight.
6. A matted polyvinyl chloride resin composition according to claim 1 wherein said (meth) acrylate is selected from the group consisting of C (meth) acrylic acid 1-6 The alkyl ester is preferably selected from methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate or a mixture of two or more thereof.
7. A matted polyvinyl chloride resin composition according to claim 1 wherein said resin composition comprises 1.5 to 4.5 parts by weight, more preferably 2 to 4 parts by weight, of a plasticizer; 2.5-3.5 weight parts of processing aid.
8. A matted polyvinyl chloride resin composition according to claim 1 wherein said resin composition comprises:
9. a rigid plastic article obtained from the matte polyvinyl chloride resin composition as set forth in any of claims 1 to 8, having an Izod impact strength of 19KJ/m 2 Or higher.
10. Use of the delustered polyvinyl chloride resin combination of any one of claims 1 to 8 in forming automotive instrument panels, automotive hard interior trim materials, portable medical device housings, electronic product housings, outdoor sports equipment.
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| CN115819901A (en) * | 2022-12-29 | 2023-03-21 | 安徽天安新材料有限公司 | High-temperature non-grain non-shiny matte film and preparation method thereof |
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| JP2002293952A (en) * | 2001-03-30 | 2002-10-09 | Shin Etsu Polymer Co Ltd | Interior material for vehicle having excellent matte appearance |
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| CN115819901A (en) * | 2022-12-29 | 2023-03-21 | 安徽天安新材料有限公司 | High-temperature non-grain non-shiny matte film and preparation method thereof |
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