CN114702679B - Active long-chain alkyl modified polysiloxane auxiliary agent for plastics and preparation method thereof - Google Patents
Active long-chain alkyl modified polysiloxane auxiliary agent for plastics and preparation method thereof Download PDFInfo
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- CN114702679B CN114702679B CN202210531902.2A CN202210531902A CN114702679B CN 114702679 B CN114702679 B CN 114702679B CN 202210531902 A CN202210531902 A CN 202210531902A CN 114702679 B CN114702679 B CN 114702679B
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- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 122
- -1 polysiloxane Polymers 0.000 title claims abstract description 118
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 67
- 229920003023 plastic Polymers 0.000 title claims abstract description 59
- 239000004033 plastic Substances 0.000 title claims abstract description 59
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 32
- 230000000996 additive effect Effects 0.000 claims abstract description 24
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 125000000962 organic group Chemical group 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 125000000524 functional group Chemical group 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 239000003085 diluting agent Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 238000012545 processing Methods 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 7
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 description 48
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 37
- 229920002554 vinyl polymer Polymers 0.000 description 37
- 239000000047 product Substances 0.000 description 19
- 230000032683 aging Effects 0.000 description 17
- 238000012360 testing method Methods 0.000 description 17
- 239000002994 raw material Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 238000001125 extrusion Methods 0.000 description 14
- 125000003545 alkoxy group Chemical group 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- URRRJXFWOUCKSG-UHFFFAOYSA-M ethanol;tetramethylazanium;hydroxide Chemical compound [OH-].CCO.C[N+](C)(C)C URRRJXFWOUCKSG-UHFFFAOYSA-M 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 238000001556 precipitation Methods 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 229910052710 silicon Inorganic materials 0.000 description 10
- 239000010703 silicon Substances 0.000 description 10
- 230000008859 change Effects 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- 238000007790 scraping Methods 0.000 description 9
- 229920002545 silicone oil Polymers 0.000 description 9
- 238000009472 formulation Methods 0.000 description 8
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 238000001746 injection moulding Methods 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 150000001408 amides Chemical class 0.000 description 7
- ILRSCQWREDREME-UHFFFAOYSA-N dodecanamide Chemical compound CCCCCCCCCCCC(N)=O ILRSCQWREDREME-UHFFFAOYSA-N 0.000 description 7
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 7
- 239000004593 Epoxy Substances 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 6
- 239000002671 adjuvant Substances 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 235000013877 carbamide Nutrition 0.000 description 6
- IRHTZOCLLONTOC-UHFFFAOYSA-N hexacosan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCCO IRHTZOCLLONTOC-UHFFFAOYSA-N 0.000 description 6
- 229920005669 high impact polystyrene Polymers 0.000 description 6
- 239000004797 high-impact polystyrene Substances 0.000 description 6
- 229920002647 polyamide Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 5
- 125000005843 halogen group Chemical group 0.000 description 5
- 238000006459 hydrosilylation reaction Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 125000005462 imide group Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 239000004594 Masterbatch (MB) Substances 0.000 description 4
- 238000005469 granulation Methods 0.000 description 4
- 230000003179 granulation Effects 0.000 description 4
- LUOABWGXXKLFGZ-UHFFFAOYSA-N hexacosanamide Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(N)=O LUOABWGXXKLFGZ-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000012855 volatile organic compound Substances 0.000 description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 125000005529 alkyleneoxy group Chemical group 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical group CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 230000001050 lubricating effect Effects 0.000 description 2
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadec-1-ene Chemical compound CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- WPMYUUITDBHVQZ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoic acid Chemical compound CC(C)(C)C1=CC(CCC(O)=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 229920002614 Polyether block amide Polymers 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009435 amidation Effects 0.000 description 1
- 238000007112 amidation reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229920001684 low density polyethylene Polymers 0.000 description 1
- 239000004702 low-density polyethylene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003020 moisturizing effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920001558 organosilicon polymer Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920001843 polymethylhydrosiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/38—Polysiloxanes modified by chemical after-treatment
- C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
- C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
- C08L23/28—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment by reaction with halogens or compounds containing halogen
- C08L23/286—Chlorinated polyethylene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Silicon Polymers (AREA)
Abstract
The invention relates to the technical field of material modification, and discloses an active long-chain alkyl modified polysiloxane auxiliary agent for plastics and a preparation method thereof, wherein the structural formula is R 1 [R 2 R 3 SiO] m R 4 ，R 1 、R 2 、R 3 、R 4 Are mutually independent monovalent organic groups or hydrogen atoms; m is an integer greater than 1. The invention provides an active long-chain alkyl modified polysiloxane additive for plastics and a preparation method thereof, aiming at achieving the purpose that the active long-chain alkyl modified polysiloxane is used as a plastic processing additive, can effectively improve the surface performance of plastic processing and plastic products, and reduces the addition amount of VOC and the additive in the plastic products.
Description
Technical Field
The invention relates to the technical field of material modification, in particular to an active long-chain alkyl modified polysiloxane auxiliary agent for plastics and a preparation method thereof.
Background
Plastics have been widely used in people's clothing and eating and housing for a long time, and especially the engineering plastics involved therein have irreplaceable positions in the fields of aviation manufacturing, transportation, building industry, food industry, electronic and electrical industry and the like due to the advantages of excellent mechanical properties, light weight and low price. However, at present, plastics belong to a large number of products, the cost of raw materials is relatively fixed, and the profit of the plastic products is continuously reduced along with the increase of market supply, which requires that enterprises further develop and obtain high-performance plastic products while improving production efficiency, and accordingly, the plastic product manufacturers can survive.
Nowadays, in the plastic processing process, a lot of additives are usually added to improve the processability of plastics; the amide auxiliary agent is widely used as a lubricant in plastics due to high quality and low price, and has a certain improvement effect on the scratch resistance of the surface of a plastic product, and a good lubricating effect can be achieved by only adding a small amount of the amide auxiliary agent during plastic processing. However, the amide-based auxiliary agent is easy to migrate to the surface of the plastic product during plastic processing, a certain amount of amide is also precipitated on the surface of the plastic product added with the amide-based auxiliary agent when the plastic product is placed for a long time, so that the use of the plastic product is influenced, and the plastic product added with the amide-based auxiliary agent generally has higher VOC.
With the continuous development of organic silicon materials, polysiloxane with ultrahigh molecular weight is often added as a plastic processing aid in the plastic processing industry to improve the processing performance of plastics and the surface performance of plastic products; because the used polysiloxane has larger molecular weight and weaker migration capability in plastics, the dosage of the polysiloxane with ultrahigh molecular weight as a plastic processing aid is generally larger, but the price of the raw material of the organosilicon is higher, thereby undoubtedly increasing the cost of plastic products and reducing the profit of enterprises.
The active long-chain alkyl modified polysiloxane is obtained by reacting long-chain alkane containing active groups with a polysiloxane material, wherein the molecule of the polysiloxane material contains an active functional group, long-chain alkyl and an organic silicon chain, the active long-chain alkyl can strengthen the combination of a polymer and plastics, the polysiloxane cannot be separated out even if the polysiloxane is non-ultrahigh molecular weight siloxane, and meanwhile, the property of the polysiloxane can be well reflected.
The mutual modification between organosilicon and long-chain alkane has been reported in documents, for example Han Qing in the article "preparation and application of organosilicon modified polyacrylamide copolymer" prepared organosilicon modified polyacrylamide copolymer, and analyzed the physicochemical properties of the copolymer, applied to the paper making process; CN101402735A discloses a preparation method of long-chain alkyl silicone oil, which realizes the simplification of steps and processes for preparing the long-chain alkyl silicone oil, achieves the purposes of improving efficiency, reducing cost and shortening period, and meets the requirement of large-scale production; CN105218827A discloses an organic group modified ultra-high molecular weight polysiloxane and a preparation method thereof, the modified polysiloxane increases the physical compatibility with polyolefin, and simultaneously introduces unsaturated double bond energy at two ends of a chain to react with the polyolefin for grafting so as to further increase the chemical bonding with the polyolefin, thereby greatly improving the mechanical property, scratch resistance and heat resistance of the polyolefin; CN104479133A discloses a preparation method of long chain alkyl modified silicone oil, which is simple and free of pollution in the preparation process, and the obtained long chain alkyl modified silicone oil is transparent and nearly colorless; CN107129563A discloses a continuous tubular preparation method of long chain alkyl modified silicone oil, which greatly improves the stability of products and reduces the production cost; CN101434702B discloses long chain alkyl modified silicone oil and a synthesis process thereof, wherein a platinum catalyst-isopropanol-acetylacetone-ethyl acetoacetate system is adopted to facilitate milder reaction conditions and shorter reaction time of the invention; CN103992474A discloses a preparation method of hyperbranched polyamide modified organic silicon resin and a coating prepared from the resin, which improves the heat resistance and hardness of polyamide; CN104177634A discloses a preparation method of polyamide modified organic silicon resin and a coating containing the resin, and the heat resistance and the hardness of polyamide are improved; CN104004198A discloses a preparation method of a high-hardness polyamide modified organic silicon resin and a coating containing the resin, and the heat resistance and hardness of polyamide are improved; CN104592527A discloses a preparation method of a modified silicone oil surfactant for spinning, the polyether amide modified silicone oil surfactant prepared in the patent has good stability and hydrophilicity, is easier to self-emulsify, and has the characteristics of low surface energy and high activity; CN105648778A discloses a preparation method of a nonionic hydrophilic fatty amide organic silicon copolymer softener, and the prepared softener has good hand feeling, good whiteness, small color change, good use stability and hydrophilicity; CN108384015A discloses an organic silicon amide wax and a preparation method thereof, wherein the organic silicon amide wax is prepared by the reaction of fatty amine and carboxyl-containing polysiloxane and is used for improving the processing performance of plastics; CN107216458A discloses an octadecyl silicone wax and a preparation method and application thereof, wherein the octadecyl silicone wax is obtained by carrying out hydrosilylation reaction on hydrogen-terminated silicone oil with a side chain containing active hydrogen and 1-octadecene, and the prepared emulsion has the properties of proper viscosity, strong moisturizing capability, strong stability and the like; CN103232602a discloses a silicone wax and a preparation method thereof, the silicone wax has high gloss, high smoothness, no sticky feeling, high moisture retention, high skin affinity, and excellent organic material compatibility; CN110358094A discloses a long-chain alkyl polyether modified silicon wax and a preparation method thereof, wherein the long-chain alkyl polyether modified silicon wax is synthesized by carrying out hydrosilylation reaction on lateral hydrogen-containing silicon oil and allyl-terminated epoxy polyolefin, and can be directly dissolved in water to prepare emulsion without an emulsifier; CN103613717B discloses a self-emulsifying acrylic acid silicone wax protective material, a preparation method and an application thereof, wherein long-chain alkyl alpha-olefin or/and long-chain alkyl monoacrylate and polymethylhydrosiloxane are subjected to hydrosilylation to prepare an acrylic acid silicone wax polymer, and the acrylic acid silicone wax protective material has the properties of good stability, good dispersibility, environmental protection and the like.
In the above patents or documents, most of the alkyl modified polysiloxanes are prepared by hydrosilylation, the catalyst is easy to be poisoned, the introduction of nitrogen-containing active organic functional groups is not facilitated, and the hydrogen-containing polysiloxane is high in price, so that the cost is increased; in the patent of synthesizing the amide modified organic silicon wax, small molecular substances are generated during synthesis, other complicated steps are needed for removing the small molecular substances, the conversion rate of amidation is difficult to control, and the purity of the product is unstable.
Disclosure of Invention
< problems to be solved by the present invention >
The invention is used for solving the problems of complex operation, poor control degree and high cost in the existing alkyl modified polysiloxane by adopting a hydrosilylation method.
< technical solution adopted in the present invention >
Aiming at the technical problems, the invention provides the active long-chain alkyl modified polysiloxane additive for plastics and the preparation method thereof, aiming at achieving the purpose that the active long-chain alkyl modified polysiloxane is used as a plastic processing additive, can effectively improve the surface properties of plastic processing and plastic products, and reduces the VOC (volatile organic compounds) and the additive amount in the plastic products.
The specific contents are as follows:
the invention provides a reactive long-chain alkyl modified polysiloxane auxiliary agent for plastics, which has a structural formula shown as (1):
R 1 [R 2 R 3 SiO] m R 4 (1)
R 1 、R 2 、R 3 、R 4 are mutually independent monovalent organic groups or hydrogen atoms; m is an integer greater than 1;
the structure of the univalent organic group is shown as a general formula (1-1), (1-2) or (1-3),
-C a H (2a+1) (1-1)
-C b H (2b-1) (1-2)
b is an integer greater than 1;
R 5 as shown in a general formula (1-3-1),
-C c H 2c - (1-3-1)
c is an integer greater than 1;
R 6 is one of hydrogen atom, alkyl, halogenated alkyl and alkyl containing polar group; an alkyl group, a halogenated alkyl group, and an alkyl group having a polar group, wherein the number of carbon atoms is an integer of 10 to 100;
R 7 is one of hydrogen atom, amino group, imide group, alkyl group, alkoxy group, epoxy alkoxy group, carboxylic acid alkoxy group, hydroxyl group and halogen atom; in the alkyl group, the alkoxy group, the epoxy alkoxy group and the carboxylic acid alkoxy group, the number of carbon atoms is an integer greater than 1;
R 1 、R 2 、R 3 、R 4 in the formula (1), the structure of at least one substituent is shown as a general formula (1-3).
In the present invention, the substituent R 6 In the (b), the polar group is one of an amino group, an imide group, an alkoxy group, an alkyleneoxy group, a carboxylic acid alkoxy group, a hydroxyl group and a halogen atom.
Secondly, the invention provides a preparation method of the active long-chain alkyl modified polysiloxane auxiliary agent for plastics, which is prepared by catalytic reaction of polysiloxane and long-chain alkane containing active functional groups.
< technical mechanism and advantageous effects adopted by the present invention >
The invention utilizes the principle of Michael addition reaction to combine long-chain alkane containing active functional groups with polysiloxane to directly obtain the active long-chain modified organic silicon copolymer.
The slipping agent prepared by the invention has the following advantages:
(1) The synthesis process is simple, easy to operate and belongs to one-step reaction, and no small molecular substance is generated;
(2) The synthetic raw materials are simple and easy to obtain, and the method is favorable for the large-scale production of products;
(3) The active long-chain alkyl is combined with polysiloxane, the long-chain alkyl and the active functional group can strengthen the combination of the polymer and the plastic, the polymer can not be separated out even if the polymer is not ultrahigh molecular weight, and meanwhile, the performance of the organic silicon can be well embodied;
(4) The combination degree of the modified polymer and the plastic is controlled by adjusting the type of the active functional group and the length of the alkyl chain, the surface enrichment degree of the polymer can be adjusted when different plastics are processed, and different processing performance, extrusion performance and scratch resistance can be achieved;
(5) The active long-chain alkyl modified polysiloxane auxiliary agent for plastics has small addition amount, and can not be separated out on the surface of a plastic product;
(6) The active long-chain alkyl modified polysiloxane auxiliary agent for plastics has lower VOC when being applied to plastic processing.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The invention aims to provide a slipping agent and a preparation method thereof, and a film opening slipping master batch and a preparation method thereof.
The invention provides a reactive long-chain alkyl modified polysiloxane auxiliary agent for plastics, which has a structural formula shown in (1):
R 1 [R 2 R 3 SiO] m R 4 (1)
R 1 、R 2 、R 3 、R 4 are mutually independent monovalent organic groups or hydrogen atoms; m is an integer greater than 1;
the structure of the univalent organic group is shown as a general formula (1-1), (1-2) or (1-3),
-C a H (2a+1) (1-1)
-C b H (2b-1) (1-2)
b is an integer greater than 1;
R 5 as shown in a general formula (1-3-1),
-C c H 2c - (1-3-1)
c is an integer greater than 1;
R 6 is one of hydrogen atom, alkyl, halogenated alkyl and alkyl containing polar group; an alkyl group, a halogenated alkyl group, and an alkyl group having a polar group, wherein the number of carbon atoms is an integer of 10 to 100;
R 7 is one of hydrogen atom, amino group, imide group, alkyl group, alkoxy group, epoxy alkoxy group, carboxylic acid alkoxy group, hydroxyl group and halogen atom; in the alkyl group, the alkoxy group, the epoxy alkoxy group and the carboxylic acid alkoxy group, the number of carbon atoms is an integer greater than 1;
R 1 、R 2 、R 3 、R 4 in (1) toThe structure with one less substituent is shown as a general formula (1-3).
In the present invention, the substituent R 6 In the (b), the polar group is one of an amino group, an imide group, an alkoxy group, an alkyleneoxy group, a carboxylic acid alkoxy group, a hydroxyl group and a halogen atom.
Secondly, the invention provides a preparation method of an active long-chain alkyl modified polysiloxane auxiliary agent for plastics, which is prepared by catalytic reaction of polysiloxane and long-chain alkane containing active functional groups.
In the present invention, the polysiloxane has a structure represented by the general formula (2):
R 8 [R 9 R 10 SiO] n R 11 (2)
R 8 、R 9 、R 10 、R 11 are mutually independent monovalent organic groups or hydrogen atoms; n is an integer greater than 1;
the structure of the monovalent organic group is general formula (1-1) or (1-2);
R 8 、R 9 、R 10 、R 11 wherein at least one substituent has an organic group represented by the general formula (1-2).
In the invention, the structural formula of the long-chain alkane containing the active functional group is shown as follows,
R 6 、R 7 are mutually independent atoms and/or groups,
R 6 is one of hydrogen atom, alkyl, halogenated alkyl and alkyl containing polar group; an alkyl group, a halogenated alkyl group, and a polar group-containing alkyl group, wherein the number of carbon atoms is an integer of 10 to 100;
R 7 is one of hydrogen atom, amino group, imide group, alkyl group, alkoxy group, epoxy alkoxy group, carboxylic acid alkoxy group, hydroxyl group and halogen atom; the number of carbon atoms in the alkyl group, alkoxy group, epoxyalkoxy group, and carboxylic acid alkoxy group is an integer greater than 1.
In the invention, polysiloxane and long-chain alkane containing active functional groups are subjected to catalytic reaction for 8-20 h at the temperature of 90-150 ℃ and the rotating speed of 150-300 r/min.
In the invention, the catalyst selected for the catalytic reaction is selected from one of sodium ethoxide, sodium hydride, tetramethylammonium hydroxide and tetrabutylammonium hydroxide.
In the invention, the dosage of the catalyst is 0.1-2% of the total reaction amount of the polysiloxane and the long-chain alkane containing the active functional group.
In the invention, the catalyst is diluted by a diluent and then used, and the catalyst comprises at least one of methanol, ethanol, isopropanol and cyclohexane.
In the invention, the reaction molar ratio of polysiloxane to long-chain alkane containing active functional groups is 1-99.
< example >
The proportions of the components in the examples are shown in Table 1.
Wherein:
a is a long-chain alkane, A1 is dodecanoamide (examples 1-3), A2 is octadecanamide (examples 4-6), A3 is hexacosanoamide (examples 7-9), A4 is tetracarboxamide (examples 10-12);
b is a polysiloxane, and the polysiloxanes referred to in examples 1 to 12 are vinyl-containing polysiloxanes;
the proportion of A and B is mole ratio;
x, y and n are integers more than 1.
Example 1
Respectively reducing the pressure of the dodecanoic acid amide and the vinyl-containing polysiloxane at the temperature of 100 ℃ and the pressure of-0.085 MPa for 2 hours to obtain reduced raw materials for later use; adding the decacarbamide and the vinyl-containing polysiloxane into a flask according to the mol ratio of 1:1, stirring for 1h at 85 ℃ and the rotation speed of 200r/min, slowly dripping 20wt% of tetramethylammonium hydroxide ethanol solution containing 0.5% of the total mass of the dodecacarbamide and the vinyl-containing polysiloxane after uniformly stirring, uniformly stirring at 85 ℃ and the rotation speed of 200r/min, heating to 150 ℃, stirring and reacting for 18h at the rotation speed of 250r/min, and obtaining the modified polysiloxane additive 1 after the reaction is finished.
Example 2
Respectively reducing the pressure of the dodecanoic acid amide and the vinyl-containing polysiloxane at the temperature of 100 ℃ and the pressure of-0.085 MPa for 2 hours to obtain reduced raw materials for later use; adding the decacarbamide and the vinyl-containing polysiloxane into a flask according to the mol ratio of 2:1, stirring for 1h at 85 ℃ and the rotation speed of 200r/min, slowly dripping 20wt% of a tetramethylammonium hydroxide ethanol solution containing 0.5% of the total mass of the dodecacarbamide and the vinyl-containing polysiloxane after uniformly stirring, uniformly stirring at 85 ℃ and the rotation speed of 200r/min, heating to 150 ℃, stirring and reacting for 18h at the rotation speed of 250r/min, and obtaining the modified polysiloxane additive 2 after the reaction is finished.
Example 3
Respectively reducing the pressure of the dodecanoamide and the vinyl-containing polysiloxane at the temperature of 100 ℃ and the pressure of-0.085 MPa for 2 hours to obtain reduced raw materials for later use; adding the decacarbamide and the vinyl-containing polysiloxane into a flask according to the mol ratio of 3:1, stirring for 1h at 85 ℃ and the rotation speed of 200r/min, slowly dripping 20wt% of a tetramethylammonium hydroxide ethanol solution containing 0.5% of the total mass of the dodecacarbamide and the vinyl-containing polysiloxane after uniformly stirring, uniformly stirring at 85 ℃ and the rotation speed of 200r/min, heating to 150 ℃, stirring and reacting for 18h at the rotation speed of 250r/min, and obtaining the modified polysiloxane additive 3 after the reaction is finished.
Example 4
Respectively reducing the pressure of the octadecanamide and the vinyl-containing polysiloxane at the temperature of 100 ℃ and the pressure of-0.085 MPa for 2h to obtain reduced raw materials for later use; adding the decarburized octadecanamide and the vinyl-containing polysiloxane into a flask according to the mol ratio of 1:1, stirring for 1h at 85 ℃ and the rotation speed of 200r/min, slowly dripping 20wt% of tetramethylammonium hydroxide ethanol solution containing 0.5% of the total mass of the dodecanoamide and the vinyl-containing polysiloxane after uniform stirring, stirring uniformly at 85 ℃ and the rotation speed of 200r/min, heating to 150 ℃, stirring and reacting for 18h at the rotation speed of 250r/min, and obtaining the modified polysiloxane additive 4 after the reaction is finished.
Example 5
Respectively reducing the pressure of the octadecanamide and the vinyl-containing polysiloxane at the temperature of 100 ℃ and the pressure of-0.085 MPa for 2h to obtain reduced raw materials for later use; adding the decarburized octadecanamide and the vinyl-containing polysiloxane into a flask according to the mol ratio of 2:1, stirring for 1h at 85 ℃ and the rotation speed of 200r/min, slowly dripping 20wt% of tetramethylammonium hydroxide ethanol solution containing 0.5% of the total mass of the dodecanoamide and the vinyl-containing polysiloxane after uniform stirring, stirring uniformly at 85 ℃ and the rotation speed of 200r/min, heating to 150 ℃, stirring and reacting for 18h at the rotation speed of 250r/min, and obtaining the modified polysiloxane additive 5 after the reaction is finished.
Example 6
Respectively reducing the pressure of the octadecanamide and the vinyl-containing polysiloxane at the temperature of 100 ℃ and the pressure of-0.085 MPa for 2h to obtain reduced raw materials for later use; adding the decarburized octadecanamide and the vinyl-containing polysiloxane into a flask according to the mol ratio of 3:1, stirring for 1h at 85 ℃ and the rotation speed of 200r/min, slowly dripping 20wt% of tetramethylammonium hydroxide ethanol solution containing 0.5% of the total mass of the dodecanoamide and the vinyl-containing polysiloxane after uniform stirring, stirring uniformly at 85 ℃ and the rotation speed of 200r/min, heating to 150 ℃, stirring and reacting for 18h at the rotation speed of 250r/min, and obtaining the modified polysiloxane additive 6 after the reaction is finished.
Example 7
Respectively reducing the hexacosanol and the vinyl-containing polysiloxane at the temperature of 100 ℃ and the pressure of-0.085 MPa for 2 hours to obtain reduced raw materials for later use; adding the reduced hexacosanamide and the vinyl-containing polysiloxane into a flask according to the mol ratio of 1:1, stirring for 1h at 85 ℃ and the rotation speed of 200r/min, slowly dripping 20wt% of a tetramethylammonium hydroxide ethanol solution containing 0.5% of the total mass of the dodecamide and the vinyl-containing polysiloxane after uniform stirring, stirring uniformly at 85 ℃ and the rotation speed of 200r/min, heating to 150 ℃, stirring and reacting for 18h at the rotation speed of 250r/min, and obtaining the modified polysiloxane additive 7 after the reaction is finished.
Example 8
Respectively reducing the hexacosanol and the vinyl-containing polysiloxane at the temperature of 100 ℃ and the pressure of-0.085 MPa for 2 hours to obtain reduced raw materials for later use; adding the reduced hexacosanamide and the vinyl-containing polysiloxane into a flask according to the mol ratio of 2:1, stirring for 1h at 85 ℃ and the rotation speed of 200r/min, slowly dripping 20wt% of a tetramethylammonium hydroxide ethanol solution containing 0.5% of the total mass of the dodecamide and the vinyl-containing polysiloxane after uniform stirring, stirring uniformly at 85 ℃ and the rotation speed of 200r/min, heating to 150 ℃, stirring and reacting for 18h at the rotation speed of 250r/min, and obtaining the modified polysiloxane additive 8 after the reaction is finished.
Example 9
Respectively reducing the hexacosanol and the vinyl-containing polysiloxane at the temperature of 100 ℃ and the pressure of-0.085 MPa for 2 hours to obtain reduced raw materials for later use; adding the reduced hexacosanamide and the vinyl-containing polysiloxane into a flask according to the mol ratio of 3:1, stirring for 1h at 85 ℃ and the rotation speed of 200r/min, slowly dripping 20wt% of a tetramethylammonium hydroxide ethanol solution containing 0.5% of the total mass of the dodecamide and the vinyl-containing polysiloxane after uniform stirring, stirring uniformly at 85 ℃ and the rotation speed of 200r/min, heating to 150 ℃, stirring and reacting for 18h at the rotation speed of 250r/min, and obtaining the modified polysiloxane additive 9 after the reaction is finished.
Example 10
Respectively reducing pressure of forty-four carbamide and vinyl-containing polysiloxane at 100 ℃ and under the pressure of-0.085 MPa for 2h to obtain reduced raw materials for later use; adding the reduced forty-four carbamide and the vinyl-containing polysiloxane into a flask according to the mol ratio of 1:1, stirring for 1h at 85 ℃ and the rotation speed of 200r/min, slowly dripping 20wt% of tetramethylammonium hydroxide ethanol solution containing 0.5% of the total mass of the dodecenamide and the vinyl-containing polysiloxane after uniform stirring, stirring uniformly at 85 ℃ and the rotation speed of 200r/min, heating to 150 ℃, stirring and reacting for 18h at the rotation speed of 250r/min, and obtaining the modified polysiloxane additive 10 after the reaction is finished.
Example 11
Respectively reducing pressure of forty-four carbamide and vinyl-containing polysiloxane at 100 ℃ and under the pressure of-0.085 MPa for 2h to obtain reduced raw materials for later use; adding the reduced forty-four carbamide and the vinyl-containing polysiloxane into a flask according to the mol ratio of 2:1, stirring for 1h at 85 ℃ and the rotation speed of 200r/min, slowly dripping 20wt% of tetramethylammonium hydroxide ethanol solution containing 0.5% of the total mass of the dodecenamide and the vinyl-containing polysiloxane after uniform stirring, stirring uniformly at 85 ℃ and the rotation speed of 200r/min, heating to 150 ℃, stirring and reacting for 18h at the rotation speed of 250r/min, and obtaining the modified polysiloxane additive 11 after the reaction is finished.
Example 12
Respectively reducing pressure of forty-four carbamide and vinyl-containing polysiloxane at 100 ℃ and under the pressure of-0.085 MPa for 2h to obtain reduced raw materials for later use; adding the reduced forty-four carbamide and the vinyl-containing polysiloxane into a flask according to the mol ratio of 3:1, stirring for 1h at 85 ℃ and the rotation speed of 200r/min, slowly dripping 20wt% of tetramethylammonium hydroxide ethanol solution containing 0.5% of the total mass of the dodecenamide and the vinyl-containing polysiloxane after uniform stirring, stirring uniformly at 85 ℃ and the rotation speed of 200r/min, heating to 150 ℃, stirring and reacting for 18h at the rotation speed of 250r/min, and obtaining the modified polysiloxane additive 12 after the reaction is finished.
< test example >
Test example 1 Performance test applied to PP
The modified polysiloxane additives 1-12 prepared in the examples 1-12 are applied to the processing of PP plastics, and a double-screw tester is used for extrusion granulation to investigate the change of the processing performance under the same extrusion process conditions; and after the materials are molded into sheets by an injection molding machine, carrying out thermal oxidation aging to investigate the precipitation condition. The 2Kg batches were prepared according to the formulations shown in tables 2 and 3.
TABLE 2 blending ratio of modified polysiloxane adjuvant (adjuvant for short)
Note: the antioxidant is 1010 tetra [ beta- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester; the ultraviolet absorbent is UV-P,2- (2-hydroxy-5-methylphenyl) benzotriazole.
Table 3 additive amount ratio of comparative example
The properties of the additives synthesized in the different examples and comparative examples, the extrusion properties when added to PP, and the results of the presence or absence of precipitation after thermo-oxidative aging are shown in Table 4.
TABLE 4 Effect of adjuvant State and on PP processing and thermo-oxidative aging precipitation
Description of the drawings: the extruder current was tested under the same extruder set-up parameters. The test conditions of the melt finger are 220 ℃ and 2.16 Kg; the thermo-oxidative aging test condition is that the injection molded part is placed in a thermo-oxidative aging tester at a constant temperature of 80 ℃ for 28 days, and then whether the surface of the injection molded part is separated out or not is observed.
From the results in Table 4, it can be seen that the various adjuvants of the examples have a very good lubricating effect under the same conditions.
Test example 2 Performance test applied to CPE
The modified polysiloxane auxiliary agent (auxiliary agent for short) in the examples 1-12 is applied to a CPE film, a casting film tester is used for drawing a film to prepare the CPE film, and the change of the processing performance of the CPE film under the same film drawing process condition is investigated; and testing the transparency and precipitation of the film.
The ingredients were mixed in 2Kg and the formulation is shown in Table 5.
TABLE 5 compounding ratio of additives
| Formulation of | Auxiliary agent | LDPE |
| Experimental proportions | 0.3％ | 99.7％ |
| The actual amount of the active ingredient | 6 g | 1994 g |
The properties of the polymer synthesized by the modified polysiloxane auxiliary agent (auxiliary agent for short) in different embodiments when the polymer is added into a CPE film, and whether the polymer is precipitated after being placed at a constant temperature and humidity of 60 ℃ and 80% for 30 days are shown in Table 6.
TABLE 6 Effect of adjuvants on CPE film Properties
Description of the invention: the extrusion torque was obtained under the same manufacturing process conditions.
As can be seen from Table 6, the addition of the modified polysiloxane auxiliary agent in the examples can effectively reduce the extrusion torque, has no influence on the transparency of the CPE film, and does not precipitate after constant temperature and humidity treatment.
Test example 3 Performance test applied to ABS
The modified polysiloxane additive (abbreviated as additive) in examples 1-12 is applied to the processing of ABS plastics, a twin-screw tester is used for extrusion granulation, and the change of the processing performance is inspected under the same extrusion process conditions; and carrying out thermal oxidation aging to investigate the precipitation condition and the change of the scraping resistance after the sheet is formed by injection molding through an injection molding machine.
The ingredients were dosed at 2Kg, the formulation of which is shown in table 7:
TABLE 7 compounding ratio of additives
| Formulation of | Auxiliary agent | ABS | Black master batch |
| Experimental proportions | 0.3％ | 98.7％ | 1％ |
| The actual amount of the composition | 6 g | 1974 g | 20 g |
The extrusion performance, scratch resistance and precipitation after thermo-oxidative aging of the modified polysiloxane additives obtained in different examples when added to ABS are shown in Table 8.
TABLE 8 Effect of adjuvants on ABS Properties
Description of the drawings: the melt index of the data is measured at 200 ℃ and 2.16 Kg; the scratch resistance test is to scrape a sample plate by adopting a cross-shaped scratch meter, and then the color difference (delta L) of the sample plate before and after scraping is measured and used as the representation of the scratch resistance effect; the thermo-oxidative aging test condition is that the injection molded part is placed in a thermo-oxidative aging tester at a constant temperature of 80 ℃ for 28 days, and then whether the surface of the injection molded part is separated out or not is observed.
As can be seen from Table 8, it can be seen from the above data that the addition of the modified polysiloxane auxiliary can effectively improve the processability and scratch resistance of ABS.
Test example 4 test for HIPS
The modified polysiloxane auxiliary agents in the embodiments 1-12 are applied to the processing of HIPS plastics, a double-screw experimental machine is used for extrusion granulation, and the change of the processing performance is inspected under the same extrusion process conditions; and carrying out thermal oxidation aging to investigate the precipitation condition and the change of the scraping resistance after the sheet is formed by injection molding through an injection molding machine.
The 2Kg batches were prepared according to the recipe shown in Table 9.
TABLE 9 compounding ratio of additives
| Formulation(s) | Auxiliary agent | HIPS | Black master batch |
| Experimental proportions | 0.3％ | 98.7％ | 1％ |
| The actual amount of the active ingredient | 6 g | 1974 g | 20 g |
The scratch resistance effect of the modified polysiloxane additives obtained in different examples when added to HIPS and the presence or absence of precipitation after thermal oxidative aging are shown in Table 10.
TABLE 10 Effect of the Polymer on HIPS Properties
Description of the drawings: in the scraping resistance test in the data, a cross scraping instrument is adopted to scrape the sample plate, and then the color difference (delta L) of the sample plate before and after scraping is measured and used as the representation of the scraping resistance effect; the thermo-oxidative aging test condition is that the injection molded part is placed in a thermo-oxidative aging tester at a constant temperature of 80 ℃ for 28 days, and then whether the surface of the injection molded part is separated out or not is observed.
As can be seen from Table 10, the addition of the modified polysiloxane auxiliary can effectively improve the processability and scratch resistance of HIPS.
Test example 5 testing applied to PBT
The modified polysiloxane auxiliary agents in the examples 1 to 12 are applied to the processing of PBT plastics, a double-screw tester is used for extrusion granulation, and the change of the processing performance is inspected under the same extrusion process condition; and carrying out thermal oxidation aging to investigate the precipitation condition and the change of the scraping resistance after the injection molding machine is used for injection molding into sheets.
The 2Kg batch was made with the formulation shown in Table 11:
TABLE 11 Polymer addition ratio
| Formulation of | Polymer and method of making same | PBT | Black masterbatch |
| Experimental proportions | 0.3％ | 98.7％ | 1％ |
| The actual amount of the active ingredient | 6 g | 1974 g | 20 g |
The extrusion performance, scratch resistance and precipitation after thermo-oxidative aging of the modified polysiloxane additive added into PBT in different examples are shown in Table 12:
TABLE 12 Effect of polymers on PBT Properties
Description of the drawings: the melt index of the data is measured at 235 ℃ and 2.16 Kg; the scratch resistance test is to scrape a sample plate by adopting a cross-shaped scratch meter, and then the color difference (delta L) of the sample plate before and after scraping is measured and used as the representation of the scratch resistance effect; the thermo-oxidative aging test condition is that the injection molded part is placed in a thermo-oxidative aging tester at a constant temperature of 80 ℃ for 28 days, and then whether the surface of the injection molded part is separated out or not is observed.
As can be seen from Table 12, the addition of the modified polysiloxane additive can effectively improve the processability and scratch resistance of PBT.
In conclusion, the modified organic silicon polymer prepared by the invention can effectively improve the processing performance and the scratch resistance of thermoplastic plastics and has no influence on the surface of an injection molding part.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. An active long-chain alkyl modified polysiloxane auxiliary agent for plastics is characterized in that the structural formula is shown as (1):
R 1 [R 2 R 3 SiO] m R 4 （1）
R 1 is a monovalent organic radical, R 1 Represented by the general formula (1-3) in a monovalent organic group;
R 4 is a monovalent organic group or a hydrogen atom;
m is an integer greater than 1;
the structure of the univalent organic group is shown as a general formula (1-1) or (1-3),
R 5 as shown in a general formula (1-3-1),
a is an integer greater than 1;
c is an integer greater than 1;
R 6 is hydrogen atom or alkyl; in the alkyl group, the number of carbon atoms is an integer of 10 to 100;
R 7 is amino;
R 2 and R 3 Is selected from-CH 3 。
2. The preparation method of the active long-chain alkyl modified polysiloxane auxiliary agent for plastics as claimed in claim 1, which is characterized in that the auxiliary agent is prepared by the catalytic reaction of polysiloxane and long-chain alkane containing active functional groups;
the polysiloxane has a structure shown in a general formula (2):
R 8 [R 9 R 10 SiO] n R 11 （2）
R 8 、R 11 are mutually independent monovalent organic groups or hydrogen atoms; n is an integer greater than 1;
the structure of the monovalent organic group is general formula (1-1);
a is an integer greater than 1;
R 9 、R 10 is selected from-CH 3 ；
The structural formula of the long-chain alkane containing the active functional group is shown as follows,
R 6 、R 7 are independent atoms and/or groups,
R 6 is hydrogen atom or alkyl; in the alkyl group, the number of carbon atoms is an integer of 10 to 100;
R 7 is an amino group.
3. The preparation method of the active long-chain alkyl modified polysiloxane auxiliary agent for plastics as claimed in claim 2, wherein the polysiloxane is prepared by catalytic reaction of the polysiloxane and long-chain alkane containing active functional groups for 8-20 h at 90-150 ℃ and at a rotation speed of 150-300 r/min.
4. The method for preparing an activated long-chain alkyl modified polysiloxane auxiliary agent for plastics according to claim 2, wherein the catalyst used for the catalytic reaction is selected from one of sodium ethoxide, sodium hydride, tetramethylammonium hydroxide and tetrabutylammonium hydroxide.
5. The method for preparing the active long-chain alkyl modified polysiloxane auxiliary agent for plastics as claimed in claim 4, wherein the dosage of the catalyst is 0.1 to 2 percent of the total reaction amount of the polysiloxane and the long-chain alkane containing the active functional group.
6. The method for preparing the reactive long-chain alkyl modified polysiloxane auxiliary agent for plastics according to claim 4, wherein the catalyst is diluted by a diluent, and the diluent comprises at least one of methanol, ethanol, isopropanol and cyclohexane.
7. The method for preparing an active long-chain alkyl modified polysiloxane additive for plastics according to any one of claims 2 to 6, wherein the reaction molar ratio of the polysiloxane to the long-chain alkane containing an active functional group is 1 to 99.
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| CN104619796A (en) * | 2012-09-21 | 2015-05-13 | 道康宁东丽株式会社 | Surface treatment agent for optical material, and optical material |
| CN104177620A (en) * | 2014-07-26 | 2014-12-03 | 张家港格瑞特化学有限公司 | Polyfunctional-group-modified polysiloxane emulsifier and preparation method thereof |
| CN106977722A (en) * | 2017-04-01 | 2017-07-25 | 广州天赐有机硅科技有限公司 | A kind of modified polyorganosiloxane of active group end-blocking and its preparation method and application |
| CN110684196A (en) * | 2019-10-30 | 2020-01-14 | 岳阳凯门水性助剂有限公司 | Polycarboxy modified silicone oil, preparation method and application thereof, and antirust agent containing same |
| CN112979962A (en) * | 2021-02-04 | 2021-06-18 | 成都思立可科技有限公司 | Branched-chain type organic silicon modified polyurethane elastomer and preparation method thereof |
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