CN115703901B - ABS resin processing aid, preparation method thereof and ABS resin composite processing aid - Google Patents
ABS resin processing aid, preparation method thereof and ABS resin composite processing aid Download PDFInfo
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- CN115703901B CN115703901B CN202110916214.3A CN202110916214A CN115703901B CN 115703901 B CN115703901 B CN 115703901B CN 202110916214 A CN202110916214 A CN 202110916214A CN 115703901 B CN115703901 B CN 115703901B
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- monoacrylate
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 65
- 239000006057 Non-nutritive feed additive Substances 0.000 title claims abstract description 57
- 239000000805 composite resin Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 113
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 96
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000005886 esterification reaction Methods 0.000 claims abstract description 15
- 230000002140 halogenating effect Effects 0.000 claims abstract description 15
- BOCLKUCIZOXUEY-UHFFFAOYSA-N 4-[tris(4-hydroxyphenyl)methyl]phenol Chemical compound C1=CC(O)=CC=C1C(C=1C=CC(O)=CC=1)(C=1C=CC(O)=CC=1)C1=CC=C(O)C=C1 BOCLKUCIZOXUEY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 6
- 239000012467 final product Substances 0.000 claims abstract description 4
- 239000002131 composite material Substances 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical group ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 20
- USPWUOFNOTUBAD-UHFFFAOYSA-N 1,2,3,4,5-pentafluoro-6-(trifluoromethyl)benzene Chemical compound FC1=C(F)C(F)=C(C(F)(F)F)C(F)=C1F USPWUOFNOTUBAD-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 9
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 6
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 6
- 235000013539 calcium stearate Nutrition 0.000 claims description 6
- 239000008116 calcium stearate Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 5
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 5
- 235000019359 magnesium stearate Nutrition 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 229930185605 Bisphenol Natural products 0.000 abstract description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 11
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 239000012752 auxiliary agent Substances 0.000 description 23
- -1 acryl groups Chemical group 0.000 description 15
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 238000012545 processing Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 150000003254 radicals Chemical class 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 239000002671 adjuvant Substances 0.000 description 4
- 230000003712 anti-aging effect Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000018109 developmental process Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000004811 liquid chromatography Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000000087 stabilizing effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000011206 ternary composite Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- MFZAXZRJGHLULL-UHFFFAOYSA-N 2,4-ditert-butyl-6-[2-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenol Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(CCC=2C(=C(C=C(C=2)C(C)(C)C)C(C)(C)C)O)=C1O MFZAXZRJGHLULL-UHFFFAOYSA-N 0.000 description 1
- GJDRKHHGPHLVNI-UHFFFAOYSA-N 2,6-ditert-butyl-4-(diethoxyphosphorylmethyl)phenol Chemical compound CCOP(=O)(OCC)CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 GJDRKHHGPHLVNI-UHFFFAOYSA-N 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229920005669 high impact polystyrene Polymers 0.000 description 1
- 239000004797 high-impact polystyrene Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 238000010094 polymer processing Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000011178 triphosphate Nutrition 0.000 description 1
- 239000001226 triphosphate Substances 0.000 description 1
- UNXRWKVEANCORM-UHFFFAOYSA-N triphosphoric acid Chemical compound OP(O)(=O)OP(O)(=O)OP(O)(O)=O UNXRWKVEANCORM-UHFFFAOYSA-N 0.000 description 1
- MGMXGCZJYUCMGY-UHFFFAOYSA-N tris(4-nonylphenyl) phosphite Chemical group C1=CC(CCCCCCCCC)=CC=C1OP(OC=1C=CC(CCCCCCCCC)=CC=1)OC1=CC=C(CCCCCCCCC)C=C1 MGMXGCZJYUCMGY-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to an ABS resin processing aid, which is a tetraphenol monoacrylate antioxidant. The invention also relates to a preparation method of the ABS resin processing aid, which comprises the following steps: dissolving tetra (4-hydroxyphenyl) methane, acrylic acid and a halogenating agent in an organic solvent, carrying out esterification reaction under the action of a catalyst, and recrystallizing a reaction product to obtain a final product. The invention also relates to an ABS resin composite processing aid, which comprises the following components: tetraphenol monoacrylate antioxidant, primary antioxidant, secondary antioxidant and stearate. Compared with bisphenol monoacrylate antioxidant, the ABS resin processing aid has the advantages of larger molecular weight, more stable state, stronger intramolecular hydrogen bond and stronger synergistic effect when being compounded with other antioxidants.
Description
Technical Field
The invention belongs to the field of ABS resin processing, and particularly relates to an ABS resin processing aid, a preparation method thereof and an ABS resin composite processing aid.
Background
ABS resin is a large-variety engineering plastic with excellent comprehensive performance, and is widely used in the fields of machinery, automobiles, electronics, building material industry and the like, and the market demand is increasing. China has become the largest polymer material producing country and consuming country worldwide. The demand of ABS resin in 2020 reaches 6X 10 3 kt, which greatly drives the industry development of auxiliary agents, and the increase of domestic polyolefin planning scale in 2020-2025 is predicted to exceed 2000 ten thousand tons per year, and the demand of antioxidant is greatly increased by more than 40%.
The development trend of the chemical auxiliary agent of the polymer material in the future is high efficiency, compounding and environmental protection. The composite auxiliary agent is a blend of various polymer material chemical auxiliary agents, and aims to enable the polymer material chemical auxiliary agents to have multifunction and enhance synergistic effect, so that the application is simple and convenient. In recent years, with the intensive study of the mechanism between compound antioxidants, the intramolecular compound antioxidant has become a great hotspot in the field of antioxidant development and application, wherein bisphenol monoacrylate antioxidants are used as carbon free radical capturing agents, double bonds on acryl groups and phenolic hydroxyl groups on benzene rings are effective active groups of the antioxidants, and the difunctional group stabilization mechanism of intramolecular hydrogen bonding between carbonyl oxygen and the phenolic hydroxyl groups enables the difunctional group stabilization mechanism to act on free radicals before the free radicals are peroxidized, so that the oxidation process of active substances is directly blocked, the free radicals are captured, and the problem of oxidative degradation of materials is solved from the source. The ternary combination with the conventional hindered phenol antioxidant and phosphite antioxidant can effectively prolong the gelation time and delay the yellowing time of the product, has excellent performance in inhibiting the polymer processing heat aging, and has good industrial prospect.
At present, the common intramolecular composite auxiliary agent mostly uses single bisphenol monoacrylate, for example Zhu Jifang uses 2, 2-ethylene (4, 6-di-tert-amyl) phenol, acrylic acid and the like as raw materials to synthesize an antioxidant KY-500, and is used for butadiene polymers as the antioxidant. However, the reaction has the problems of low yield and poor economy. The invention application CN101148408A discloses a preparation method of bisphenol monoacrylate compound antioxidant, which adopts a one-step synthesis process, takes bisphenol compound, acrylic acid and phosphorus oxychloride as raw materials, triethylamine as acid absorbent and aliphatic hydrocarbon or aromatic hydrocarbon as solvent, and generates bisphenol monoacrylate compound antioxidant through acyl chlorination and esterification reaction; wherein the bisphenol compound is: 2,2' -ethylenebis (4, 6-di-tertepentylphenol); 2,2' -ethylenebis (4, 6-di-tert-butylphenol); the aliphatic hydrocarbon solvent is aliphatic hydrocarbon of C6-C8; C6-C8 aromatic hydrocarbon; the bisphenol monoacrylate compound antioxidant product is: 2- [1- (2-hydroxy-3, 5-ditetrapentylphenyl) -ethyl ] -4, 6-ditetrapentylphenyl acrylate, 2- [1- (2-hydroxy-3, 5-ditetrabutylphenyl) -ethyl ] -4, 6-ditetrabutylphenyl acrylate, characterized in that the molar ratio of bisphenol compound to acrylic acid is 1:1.0-1.2; the molar ratio of the acrylic acid to the phosphorus oxychloride is 3:1.0-1.2; the mol ratio of the phosphorus oxychloride to the triethylamine is 1:3.0-4.0; wherein phosphorus oxychloride is fed in a dropwise manner; the triethylamine is fed in a dropwise manner. But the molecular mass and the intramolecular hydrogen bonding acting force are smaller. Therefore, the development direction of adding other types of functional groups of the intramolecular composite auxiliary agent is started, and as disclosed in the application CN110183364A, a thioether bisphenol acrylic ester multi-effect antioxidant and a preparation method thereof are disclosed, wherein the antioxidant has a molecular structure shown in the following formula:
Wherein R 1 is a C1-C5 linear or branched alkyl group, and R 2 is a C1-C5 linear or branched alkyl group. However, there is also a problem that the molecular mass is small, and extraction resistance and migration resistance are small. The invention application CN108299496A discloses an antioxidant containing organic phosphite and a synthesis method, wherein the antioxidant containing organic phosphite is named as follows: the dipentaerythritol fatty alcohol triphosphate has the molecular structural formula:
The molecular weight is as follows: 1148; the phosphorus content is: 8.1%. However, the reaction process is complicated and the reaction temperature is high. The invention application CN101824202A discloses a composite processing stabilizer for ABS and HIPS resin, which consists of the following raw materials in percentage by mass: 5-90% of bisphenol monoacrylic acid antioxidant, 5-90% of phenolic antioxidant and 5-90% of auxiliary antioxidant, wherein the bisphenol monoacrylic acid antioxidant is KY-500, the phenolic antioxidant is antioxidant 1076, antioxidant 1010, antioxidant WSL, antioxidant 300, antioxidant 245, antioxidant 1035 and antioxidant 1222, and the auxiliary antioxidant is TNPP, antioxidant 168, P-EPQ, antioxidant 626, DLTP and DSTP. However, there are problems of complex compounding process and poor economy.
Disclosure of Invention
Based on the foregoing, it is an object of the present invention to provide a processing aid capable of enhancing the oxidation resistance of an ABS resin in a processed state and a method for preparing the same. The processing aid tetraphenol monoacrylate antioxidant has three molecular phenolic hydroxyl groups similar to antioxidant 1010 and acrylic acid groups with double bonds, so that intramolecular hydrogen bonds are enhanced, and better extraction resistance and migration resistance are realized.
Another object of the present invention is to provide a composite processing aid capable of enhancing the oxidation resistance of ABS resin in a processing state, wherein the composite processing aid comprises a tetraphenol monoacrylate antioxidant, a main antioxidant and an auxiliary antioxidant, and the tetraphenol monoacrylate antioxidant has three phenolic hydroxyl groups similar to antioxidant 1010 and an acrylic group with double bonds, so that intramolecular hydrogen bonds are enhanced, better extraction resistance and migration resistance are provided, and the tetraphenol monoacrylate antioxidant and other antioxidants can generate stronger synergistic effect to enhance the oxidation resistance of ABS, and meanwhile, the composite processing aid can also effectively enhance the properties such as yellow index of ABS resin, and the like, and can be applied to other resins besides ABS.
In order to achieve the above purpose, the invention provides an ABS resin processing aid, which is a tetraphenol monoacrylate antioxidant.
The ABS resin processing aid disclosed by the invention is preferable in that the structure of the tetraphenol monoacrylate antioxidant is shown as a formula I:
in order to achieve the above purpose, the invention also provides a preparation method of the ABS resin processing aid, which comprises the following steps:
Dissolving tetra (4-hydroxyphenyl) methane, acrylic acid and a halogenating agent in an organic solvent, carrying out esterification reaction under the action of a catalyst, and recrystallizing a reaction product to obtain a final product;
wherein the molar ratio of the tetra (4-hydroxyphenyl) methane, the acrylic acid and the halogenating agent is 1:1.25-1.5:0.3-0.4; the mol ratio of the halogenating agent to the catalyst is 1:3.0-4.0.
The preparation method of the ABS resin processing aid is characterized in that the halogenating agent is phosphorus oxychloride, and the catalyst is triethylamine.
The preparation method of the ABS resin processing aid is characterized in that the organic solvent is preferably one of octafluorotoluene, n-heptane or toluene.
The preparation method of the ABS resin processing aid provided by the invention is characterized in that the esterification reaction conditions are as follows: the temperature is 75-85 ℃ and the time is 2-2.5 h; and the yield of the esterification reaction is more than 87wt%.
Specifically, the preparation method of the ABS resin processing aid comprises the steps that tetra (4-hydroxyphenyl) methane, acrylic acid and a halogenating agent are dissolved in an organic solvent, and under the action of a catalyst, the product is prepared by one-step;
Further, the esterification reaction has the following reaction formula:
In order to achieve the above purpose, the invention also provides an ABS resin composite processing aid, which comprises the following components:
10 to 30 weight percent of tetraphenol monoacrylate antioxidant,
20 To 40wt%, preferably 20 to 35wt%,
10-30Wt%, preferably 20-30wt% of auxiliary antioxidant
20-30Wt% of stearate.
The ABS resin composite processing aid of the invention is preferable in that the main antioxidant is antioxidant 3114 and/or antioxidant 1010.
The ABS resin composite processing aid is preferably an antioxidant 168 and/or an antioxidant 626.
The ABS resin composite processing aid is characterized in that the stearate is at least one of magnesium stearate, zinc stearate and calcium stearate.
The ABS resin composite processing aid is preferably added in an amount of 0.3-0.55% of the total mass of the ABS resin.
Compared with the prior art, the method has the following advantages and effects:
The ABS resin processing aid tetraphenol acrylic ester antioxidant provided by the invention has three molecules of phenolic hydroxyl groups similar to antioxidant 1010 and acrylic groups with double bonds in the molecule, so that the intramolecular hydrogen bond is enhanced. After the macromolecular radicals are trapped by the acrylic groups, the intramolecular hydrogen bonds will transfer more rapidly to form stable phenolic oxygen radicals. And the antioxidant has a branched structure, so that the physical property is stable, and the molecular weight is large, and the extraction resistance and migration resistance are improved.
According to the preparation method of the ABS resin processing aid, the tetra (4-hydroxyphenyl) methane and the acrylic acid are subjected to esterification reaction in octafluorotoluene solvent, so that the tetraphenol acrylic ester antioxidant with larger molecular weight is obtained.
The four-phenol acrylate antioxidant and other antioxidants (especially hindered phenol antioxidants and phosphite antioxidants) are compounded for use to form a ternary composite processing aid stabilizing system. Compared with the traditional antioxidant, on one hand, the system is equivalent to adding an anti-aging and anti-aging line in advance, reducing the quantity of the peroxide free radicals generated subsequently and fundamentally reducing the burden of the main antioxidant and the auxiliary antioxidant; on the other hand, the advantages of the traditional antioxidant are maintained, and the cost is reduced.
In conclusion, the ABS resin processing aid tetraphenol acrylic ester antioxidant provided by the invention has larger molecular weight, more stable state and stronger intramolecular hydrogen bond, and has stronger synergistic effect when being compounded with other antioxidants; the composite processing aid not only can enhance the oxidation resistance of the ABS resin in a processing state, but also can effectively improve the properties such as yellow index and the like of the ABS resin.
Detailed Description
The following describes embodiments of the present invention in detail: the present example is implemented on the premise of the technical scheme of the present invention, and detailed implementation modes and processes are given, but the protection scope of the present invention is not limited to the following examples, and experimental methods without specific conditions are not noted in the following examples, and generally according to conventional conditions.
The ABS resin processing aid provided by the invention is a tetraphenol monoacrylate antioxidant.
In some embodiments, it is preferred that the tetraphenol monoacrylate antioxidant has the structure shown in formula I:
The preparation method of the ABS resin processing aid provided by the invention comprises the following steps:
Dissolving tetra (4-hydroxyphenyl) methane, acrylic acid and a halogenating agent in an organic solvent, carrying out esterification reaction under the action of a catalyst, and recrystallizing a reaction product to obtain a final product;
wherein the molar ratio of the tetra (4-hydroxyphenyl) methane, the acrylic acid and the halogenating agent is 1:1.25-1.5:0.3-0.4; the mol ratio of the halogenating agent to the catalyst is 1:3.0-4.0.
In some embodiments, it is preferred that the halogenating agent is phosphorus oxychloride and the catalyst is triethylamine.
In some embodiments, it is preferred that the organic solvent is one of octafluorotoluene, n-heptane, or toluene.
In some embodiments, it is preferred that the esterification reaction conditions are: the temperature is 75-85 ℃ and the time is 2-2.5 h; and the yield of the esterification reaction is more than 87wt%.
Specifically, the preparation method of the ABS resin processing aid comprises the steps that tetra (4-hydroxyphenyl) methane, acrylic acid and a halogenating agent are dissolved in an organic solvent, and under the action of a catalyst, the product is prepared by one-step;
Further, the esterification reaction has the following reaction formula:
The ABS resin composite processing aid provided by the invention comprises the following components:
10 to 30 weight percent of tetraphenol monoacrylate antioxidant,
20 To 40wt%, preferably 20 to 35wt%,
10 To 30wt%, preferably 20 to 30wt%,
20-30Wt% of stearate.
In some embodiments, it is preferred that the primary antioxidant is antioxidant 3114 and/or antioxidant 1010.
In some embodiments, it is preferred that the secondary antioxidants are antioxidants 168 and/or 626.
In some embodiments, it is preferred that the stearate is at least one of magnesium stearate, zinc stearate, and calcium stearate.
In some embodiments, it is preferable that the composite processing aid is added in an amount of 0.3 to 0.55% of the total mass of the ABS resin.
EXAMPLE 1 Synthesis of multifunctional auxiliary in tetraphenol monoacrylate molecule
68G (0.18 mol) of tetra (4-hydroxyphenyl) methane, 16.2g (0.23 mol) of acrylic acid, 18.2g (0.18 mol) of triethylamine and 150ml of octafluorotoluene are placed in a four-necked flask (500 ml) with a stirrer, a thermometer and a reflux condenser in sequence, the temperature is raised to 75 ℃ by stirring, 61.5g (after completion of dropwise addition within 35min of 0.6 mol) of phosphorus oxychloride is started to be added, and the mixture is kept for 2 hours. After the completion of the reaction, the obtained organic layer was separated as a reaction product, and analyzed by liquid chromatography. The organic phases were combined by rinsing with octafluorotoluene. The octafluorotoluene was distilled off under reduced pressure, and the remaining organic phase was recrystallized, followed by suction filtration to give 71.8g of a white product in a yield of 91% by weight.
EXAMPLE 2 Synthesis of multifunctional auxiliary in tetraphenol monoacrylate molecule
61.5G (0.16 mol) of tetrakis (4-hydroxyphenyl) methane, 17.29g (0.24 mol) of acrylic acid, 16.19g (0.16 mol) of triethylamine and octafluorotoluene (150 ml) were placed in a four-necked flask (500 ml) equipped with a stirrer, a thermometer and a reflux condenser in this order, the temperature was raised to 85℃with stirring, 41.2g (after completion of dropwise addition within 35min of 0.4 mol) of phosphorus oxychloride was started, and the mixture was kept at the temperature for 2.5 hours. After the completion of the reaction, the obtained organic layer was separated as a reaction product, and analyzed by liquid chromatography. The organic phases were combined by rinsing with octafluorotoluene. Octafluorotoluene was distilled off under reduced pressure, and the remaining organic phase was recrystallized, followed by suction filtration to give 69.43g of a white product in a yield of 88wt%.
EXAMPLE 3 Synthesis of multifunctional auxiliary in tetraphenol monoacrylate molecule
61.5G (0.16 mol) of tetrakis (4-hydroxyphenyl) methane, 14.99g (0.21 mol) of acrylic acid, 16.19g (0.16 mol) of triethylamine and octafluorotoluene (150 ml) were placed in a four-necked flask (500 ml) with a stirrer, a thermometer and a reflux condenser in this order, the temperature was raised to 80℃with stirring, 16.4g (after completion of dropwise addition within 35 min) of phosphorus oxychloride was started to be added dropwise, and the mixture was kept at that temperature for 2 hours. After the completion of the reaction, the obtained organic layer was separated as a reaction product, and analyzed by liquid chromatography. The organic phases were combined by rinsing with octafluorotoluene. The octafluorotoluene was distilled off under reduced pressure, and the remaining organic phase was recrystallized, followed by suction filtration to obtain 70.9g of a white product in a yield of 90% by weight.
Example 4 preparation of a Tetraphenol monoacrylate-containing Complex adjuvant
20G of tetraphenol monoacrylate of example 1 is weighed, 1010 g of antioxidant, 168 g of antioxidant and 20g of calcium stearate are taken and uniformly mixed to prepare the composite additive 1.
Example 5 preparation of a Compound auxiliary comprising tetraphenol monoacrylate
20G of tetraphenol monoacrylate of example 1 is weighed, 20g of antioxidant 3114, 168 g of antioxidant 40g and 20g of magnesium stearate are uniformly mixed to prepare a composite auxiliary agent 2.
Example 6 preparation of a Tetraphenol monoacrylate-containing Complex adjuvant
10G of tetraphenol monoacrylate of example 1 is weighed, 30g of antioxidant 1010, 626 and 30g of zinc stearate are taken and uniformly mixed to prepare a compound auxiliary agent 3.
Example 7 preparation of a Tetraphenol monoacrylate-containing Complex adjuvant
30G of tetraphenol monoacrylate of example 1 is weighed, 30g of antioxidant 3114, 168 g of antioxidant, 20g of zinc stearate are taken and uniformly mixed to prepare a composite auxiliary agent 4.
Example 8 preparation of a Tetraphenol monoacrylate-containing Complex adjuvant
25G of tetraphenol monoacrylate of example 1 is weighed, 1010 g of antioxidant, 168 g of antioxidant and 30g of calcium stearate are taken and uniformly mixed to prepare the composite additive 5.
Comparative example 1 preparation of bisphenol monoacrylate-containing Compound auxiliary agent
30G of bisphenol monoacrylate antioxidant is weighed, 1076 g of antioxidant, 168 g of antioxidant and 20g of calcium stearate are taken and uniformly mixed to prepare the bisphenol monoacrylate antioxidant composite auxiliary agent, and the bisphenol monoacrylate antioxidant composite auxiliary agent is recorded as a comparison composite auxiliary agent 1.
Comparative test 1:
Weighing 25g of ABS powder and 75g of SAN powder, adding 1-5 g of equivalent composite auxiliary agent, uniformly mixing, and then adding and granulating according to a preheated (the preheating temperature is 210 ℃) mixing granulating device feeding port. Then, according to GB 19466 Standard of the method for measuring the thermal stability of Plastic raw materials and the oxidation induction period, the ABS resin can be evaluated in the oxidation induction period by a Differential Scanning Calorimeter (DSC) at 160 ℃, and the yellow index is measured according to HG/T3862-2006 standard of the test method for Plastic yellow index, and the evaluation results are shown in Table 1.
Wherein, the composite auxiliary agent 6 is that the adding amount of the composite auxiliary agent 1 is only adjusted to 0.4g according to the method, and the composite auxiliary agent 7 is that the adding amount of the composite auxiliary agent 1 is only adjusted to 0.55 according to the method;
wherein, the comparison sample 1 is to replace the composite auxiliary agent 1 with the tetraphenol monoacrylate antioxidant according to the above method, the comparison sample 2 is to replace the composite auxiliary agent 1 with the bisphenol monoacrylate antioxidant according to the above method, and the comparison sample 3 is to replace the composite auxiliary agent 1 with the comparison composite auxiliary agent 1 according to the above method.
TABLE 1 ABS resin oxidation induction period Performance test
As can be seen from comparison of the comparison sample 1 and the comparison sample 2, the antioxidant of the tetraphenol acrylate serving as the ABS resin processing aid provided by the invention has better antioxidant property than the existing bisphenol monoacrylate antioxidant when being singly used.
As can be seen from comparison of the composite additives 1 to 7 and the comparison sample 3, when the ABS resin processing additive tetraphenol acrylic ester antioxidant provided by the invention is compounded with other antioxidants (especially hindered phenol antioxidants and phosphite antioxidants) for use, a ternary composite processing additive stabilizing system is formed. Compared with the traditional antioxidant, the system has more excellent oxidation resistance.
From the above, the ABS resin processing aid tetraphenol acrylic ester antioxidant provided by the invention has three molecules of phenolic hydroxyl groups similar to antioxidant 1010 and acrylic groups with double bonds in the molecule, so that the intramolecular hydrogen bond is enhanced. After the macromolecular radicals are trapped by the acrylic groups, the intramolecular hydrogen bonds will transfer more rapidly to form stable phenolic oxygen radicals. And the antioxidant has a branched structure, so that the physical property is stable, and the molecular weight is large, and the extraction resistance and migration resistance are improved.
According to the preparation method of the ABS resin processing aid, the tetra (4-hydroxyphenyl) methane and the acrylic acid are subjected to esterification reaction in octafluorotoluene solvent, so that the tetraphenol acrylic ester antioxidant with larger molecular weight is obtained.
The four-phenol acrylate antioxidant and other antioxidants (especially hindered phenol antioxidants and phosphite antioxidants) are compounded for use to form a ternary composite processing aid stabilizing system. Compared with the traditional antioxidant, on one hand, the system is equivalent to adding an anti-aging and anti-aging line in advance, reducing the quantity of the peroxide free radicals generated subsequently and fundamentally reducing the burden of the main antioxidant and the auxiliary antioxidant; on the other hand, the advantages of the traditional antioxidant are maintained, and the cost is reduced.
In conclusion, the ABS resin processing aid tetraphenol acrylic ester antioxidant provided by the invention has larger molecular weight, more stable state and stronger intramolecular hydrogen bond, and has stronger synergistic effect when being compounded with other antioxidants; the composite processing aid not only can enhance the oxidation resistance of the ABS resin in a processing state, but also can effectively improve the properties such as yellow index and the like of the ABS resin.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention.
Claims (11)
1. An ABS resin processing aid is characterized in that the processing aid is a tetraphenol monoacrylate antioxidant; the structure of the tetraphenol monoacrylate antioxidant is shown as a formula I:
2. a method for preparing the ABS resin processing aid according to claim 1, comprising the steps of:
Dissolving tetra (4-hydroxyphenyl) methane, acrylic acid and a halogenating agent in an organic solvent, carrying out esterification reaction under the action of a catalyst, and recrystallizing a reaction product to obtain a final product;
wherein the molar ratio of the tetra (4-hydroxyphenyl) methane, the acrylic acid and the halogenating agent is 1:1.25-1.5:0.3-0.4; the mol ratio of the halogenating agent to the catalyst is 1:3.0-4.0.
3. The method for preparing an ABS resin processing aid according to claim 2, wherein the halogenating agent is phosphorus oxychloride and the catalyst is triethylamine.
4. The method for producing an ABS resin processing aid according to claim 2, wherein the organic solvent is one of octafluorotoluene, n-heptane and toluene.
5. The method for producing an ABS resin processing aid according to claim 2, wherein the esterification reaction conditions are: the temperature is 75-85 ℃ and the time is 2-2.5 h; and the yield of the esterification reaction is more than 87wt%.
6. An ABS resin composite processing aid is characterized by comprising the following components:
10 to 30 weight percent of tetraphenol monoacrylate antioxidant,
20-40Wt% of main antioxidant,
10-30Wt% of auxiliary antioxidant,
20-30Wt% of stearate;
The tetraphenol monoacrylate antioxidant is the ABS resin processing aid of claim 1.
7. The ABS resin composite processing aid according to claim 6, comprising the following components:
10 to 30 weight percent of tetraphenol monoacrylate antioxidant,
20-35Wt% of main antioxidant,
20-30Wt% of auxiliary antioxidant,
20-30Wt% of stearate.
8. The ABS resin composite processing aid according to claim 6, wherein the primary antioxidant is antioxidant 3114 and/or antioxidant 1010.
9. The ABS resin composite processing aid according to claim 6, wherein the auxiliary antioxidant is an antioxidant 168 and/or an antioxidant 626.
10. The ABS resin composite processing aid according to claim 6, wherein the stearate is at least one of magnesium stearate, zinc stearate and calcium stearate.
11. The ABS resin composite processing aid according to claim 6, wherein the additive amount of the composite processing aid is 0.3 to 0.55% of the total mass of the ABS resin.
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| KR101627725B1 (en) * | 2009-02-03 | 2016-06-07 | 삼성전자 주식회사 | Photocurable compound |
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