CN115703901A - ABS (acrylonitrile butadiene styrene) resin processing aid, preparation method thereof and ABS resin composite processing aid - Google Patents
ABS (acrylonitrile butadiene styrene) resin processing aid, preparation method thereof and ABS resin composite processing aid Download PDFInfo
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- CN115703901A CN115703901A CN202110916214.3A CN202110916214A CN115703901A CN 115703901 A CN115703901 A CN 115703901A CN 202110916214 A CN202110916214 A CN 202110916214A CN 115703901 A CN115703901 A CN 115703901A
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- antioxidant
- processing aid
- abs resin
- monoacrylate
- tetraphenol
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- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 66
- 239000006057 Non-nutritive feed additive Substances 0.000 title claims abstract description 56
- 239000000805 composite resin Substances 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 22
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 title description 8
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 title description 8
- 239000011347 resin Substances 0.000 title description 4
- 229920005989 resin Polymers 0.000 title description 4
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 113
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 92
- 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 15
- 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 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 7
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 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
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 26
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical group ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- 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
- 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 8
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 claims description 8
- 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
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 5
- 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 4
- 235000019359 magnesium stearate Nutrition 0.000 claims description 4
- 229930185605 Bisphenol Natural products 0.000 abstract description 17
- 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
- 239000000654 additive Substances 0.000 description 16
- 230000000996 additive effect Effects 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- -1 2, 2-ethylene (4, 6-ditert amyl) phenol Chemical compound 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 6
- 239000012752 auxiliary agent Substances 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- STLLXWLDRUVCHL-UHFFFAOYSA-N [2-[1-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenyl] prop-2-enoate Chemical compound CCC(C)(C)C1=CC(C(C)(C)CC)=CC(C(C)C=2C(=C(C=C(C=2)C(C)(C)CC)C(C)(C)CC)OC(=O)C=C)=C1O STLLXWLDRUVCHL-UHFFFAOYSA-N 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
- 238000002156 mixing Methods 0.000 description 4
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 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
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 230000006698 induction Effects 0.000 description 3
- 238000004811 liquid chromatography Methods 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
- 239000011206 ternary composite Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002530 phenolic antioxidant Substances 0.000 description 2
- 150000008301 phosphite esters Chemical class 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
- 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
- BJCIDKUYXJXIBR-UHFFFAOYSA-N 2-[2-[2-hydroxy-3,5-bis(2-methylbutan-2-yl)phenyl]ethyl]-4,6-bis(2-methylbutan-2-yl)phenol Chemical compound C(CC1=C(C(=CC(=C1)C(C)(C)CC)C(C)(C)CC)O)C1=C(C(=CC(=C1)C(C)(C)CC)C(C)(C)CC)O BJCIDKUYXJXIBR-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
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 229940123457 Free radical scavenger Drugs 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- STBTWAHOSKIZDC-UHFFFAOYSA-N [2,4-ditert-butyl-6-[1-(3,5-ditert-butyl-2-hydroxyphenyl)ethyl]phenyl] prop-2-enoate Chemical compound C=1C(C(C)(C)C)=CC(C(C)(C)C)=C(OC(=O)C=C)C=1C(C)C1=CC(C(C)(C)C)=CC(C(C)(C)C)=C1O STBTWAHOSKIZDC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 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
- 230000001588 bifunctional effect 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
- 229910052956 cinnabar Inorganic materials 0.000 description 1
- 238000000113 differential scanning calorimetry 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
- 238000010828 elution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000010438 heat treatment 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
- 239000000203 mixture 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
- 239000012071 phase Substances 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
- 239000002516 radical scavenger Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 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
- 150000003568 thioethers Chemical class 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
- 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, main antioxidant, auxiliary antioxidant and stearate. Compared with bisphenol monoacrylate antioxidants, the ABS resin processing aid has larger molecular weight, more stable state, stronger intramolecular hydrogen bonds 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 of engineering plastics with excellent comprehensive performance, is widely applied to the fields of machinery, automobiles, electronics, building material industry and the like, and has increasing market demand. China has become the largest polymer material producing and consuming countries in the world. The domestic demand of the 2020 on ABS resin reaches 6 multiplied by 10 3 kt, which greatly drives the industrial development of the auxiliary agent, predicts that the increase scale of the domestic polyolefin plan will exceed 2000 million tons per year in 2020-2025, and the demand of the antioxidant will also be greatly increased by more than 40%.
The development trend of the chemical auxiliary agent of the polymer material in the future is to be efficient, compound and environment-friendly. The composite assistant is a blend of various polymer material chemical assistants, and aims to provide the polymer material chemical assistants with multiple functions and enhanced synergistic effect, so that the application is simple and convenient. In recent years, with the intensive research on the mechanism among the complex antioxidants, intramolecular complex antioxidants have become a great hotspot in the development and application fields of antioxidants, wherein bisphenol monoacrylate antioxidants are used as carbon free radical scavengers, double bonds on acryloyl groups and phenolic hydroxyl groups on benzene rings are effective active groups of the antioxidants, and the bifunctional stabilization mechanism of intramolecular hydrogen bond combination between carbonyl oxygen and phenolic hydroxyl groups enables the carbonyl oxygen and the phenolic hydroxyl groups to act as free radicals before the free radicals are overoxidized, directly blocks the oxidation process of active substances so as to capture the free radicals, and solves the problem of oxidative degradation of materials from the source. The product is compounded with conventional hindered phenol antioxidants and phosphite antioxidants in a ternary way, can effectively prolong the gelation time and delay the yellowing time of products, shows excellent performance in inhibiting the heat aging of polymer processing, and has good industrial prospect.
At present, a common intramolecular compound assistant mostly takes single bisphenol monoacrylate as a main component, for example, cinnabar takes 2, 2-ethylene (4, 6-ditert amyl) phenol, acrylic acid and the like as raw materials to synthesize an antioxidant KY-500, and the antioxidant KY-500 is used for a butadiene polymer as the antioxidant. However, the reaction has problems of low yield and poor economy. The invention application CN101148408A discloses a preparation method of a bisphenol monoacrylate compound antioxidant, which adopts a one-step synthesis process, takes a bisphenol compound, acrylic acid and phosphorus oxychloride as raw materials, triethylamine as an acid absorbent and aliphatic hydrocarbon or aromatic hydrocarbon as a solvent, and generates the bisphenol monoacrylate compound antioxidant through acyl chlorination and esterification reactions; wherein the bisphenol compound is: 2,2' -ethylenebis (4, 6-ditert-pentylphenol); 2,2' -ethylenebis (4, 6-di-tert-butylphenol); the aliphatic hydrocarbon solvent is aliphatic hydrocarbon of C6-C8; C6-C8 aromatic hydrocarbons; the bisphenol monoacrylate compound antioxidant product comprises: 2- [1- (2-hydroxy-3, 5-ditert-pentylphenyl) -ethyl ] -4, 6-ditert-pentylphenyl acrylate, 2- [1- (2-hydroxy-3, 5-ditert-butylphenyl) -ethyl ] -4, 6-ditert-butylphenyl acrylate, characterized in that the molar ratio of bisphenol compound to acrylic acid is 1: 1.0 to 1.2; the mol 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 the phosphorus oxychloride is fed in a dropwise manner; triethylamine is fed in a dropwise manner. But its molecular mass and intramolecular hydrogen bonding force are small. Therefore, the development direction of adding other types of functional groups to the intramolecular compound auxiliary is started, for example, the invention application CN110183364A discloses a thioether bisphenol acrylate multi-effect antioxidant and a preparation method thereof, and the antioxidant has a molecular structure shown as the following formula:
wherein R is 1 Is C1-C5 linear or branched alkyl, R 2 Is C1-C5 straight-chain or branched-chain alkyl. However, there are also problems of small molecular weight, less resistance to extraction and migration. The invention application CN108299496A discloses an antioxidant containing organic phosphite ester and a synthesis method thereof, wherein the name of the antioxidant containing organic phosphite ester is as follows: the dipentaerythritol triphosphite fatty alcohol ester has a molecular structural formula as follows:
the molecular weight is: 1148, adding a catalyst; the phosphorus content is: 8.1 percent. 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 resins, which comprises the following raw materials by mass percent: 5-90% of bisphenol monoacrylic antioxidant, 5-90% of phenolic antioxidant and 5-90% of auxiliary antioxidant, wherein the bisphenol monoacrylic 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. But has the problems of complex compounding process and poor economy.
Disclosure of Invention
Based on the above, one of the objectives of the present invention is to provide a processing aid capable of enhancing the oxidation resistance of an ABS resin in a processed state and a preparation method thereof. The processing aid tetraphenol monoacrylate antioxidant has both trimolecular phenolic hydroxyl similar to antioxidant 1010 and acrylic acid group with double bond, so that intramolecular hydrogen bond is enhanced, and the processing aid tetraphenol monoacrylate antioxidant has better extraction resistance and migration resistance.
Another aspect of the present invention is to provide a composite processing aid capable of enhancing the oxidation resistance of ABS resin in a processing state, the composite processing aid comprises a tetraphenol monoacrylate antioxidant, a primary antioxidant and a secondary antioxidant, the tetraphenol monoacrylate antioxidant has both a trimolecular phenolic hydroxyl group similar to antioxidant 1010 and an acrylic acid group with double bonds, so as to enhance intramolecular hydrogen bonds, and has better extraction resistance and migration resistance, and the tetraphenol monoacrylate antioxidant can generate stronger synergistic effect by compounding with other antioxidants to improve the oxidation resistance of ABS, and the composite aid can also effectively improve the properties of the ABS resin, such as yellow index, and can be applied to other resins besides ABS.
In order to achieve the 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 preferably characterized in that the structure of the tetraphenol monoacrylate antioxidant is shown as a formula I:
in order to achieve the above object, the present invention further provides a preparation method of the above ABS resin processing aid, comprising 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 tetra (4-hydroxyphenyl) methane, acrylic acid and halogenating agent is 1.25-1.5; the molar ratio of the halogenating agent to the catalyst is 1.
In the preparation method of the ABS resin processing aid, the halogenating agent is preferably phosphorus oxychloride, and the catalyst is triethylamine.
The preparation method of the ABS resin processing aid disclosed by the invention is preferably that the organic solvent is one of octafluorotoluene, n-heptane or toluene.
The preparation method of the ABS resin processing aid of the invention is preferably 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, in the preparation method of the ABS resin processing aid, the tetraphenol acrylate is a product prepared by dissolving tetra (4-hydroxyphenyl) methane, acrylic acid and a halogenating agent in an organic solvent through a one-step method under the action of a catalyst;
further, the reaction formula of the esterification reaction is as follows:
in order to achieve the above object, the present invention also provides an ABS resin composite processing aid, comprising the following components:
10-30wt% of tetraphenol monoacrylate antioxidant,
20-40wt%, preferably 20-35wt%,
10-30wt%, preferably 20-30wt% of auxiliary antioxidant
Stearate 20-30wt%.
The ABS resin composite processing aid disclosed by the invention is preferably used, wherein the main antioxidant is antioxidant 3114 and/or antioxidant 1010.
The ABS resin composite processing aid is preferably prepared by using an auxiliary antioxidant 168 and/or an antioxidant 626.
The ABS resin composite processing aid provided by the invention is preferably characterized in that the stearate is at least one of magnesium stearate, zinc stearate and calcium stearate.
The ABS resin composite processing aid disclosed by the invention 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 antioxidant of the four-phenol acrylate as the ABS resin processing aid provided by the invention has a trimolecular phenolic hydroxyl group similar to antioxidant 1010 in a molecule and also has an acrylic acid group with double bonds, so that an intramolecular hydrogen bond is enhanced. After the macromolecular free radical is captured by the acrylic acid group, the intramolecular hydrogen bond can be more quickly transferred to form stable phenoxy free radical. And because the antioxidant is of a branched structure, the physical property is stable, and the molecular weight is large, the extraction resistance and the migration resistance are improved.
According to the preparation method of the ABS resin processing aid, tetra (4-hydroxyphenyl) methane and acrylic acid are subjected to esterification reaction in an octafluorotoluene solvent to obtain the tetraphenol acrylate antioxidant with a large molecular weight.
In the ABS resin composite processing aid provided by the invention, the tetraphenol acrylate antioxidant and other antioxidants (particularly 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 defense line in advance, reducing the number of the subsequent generated peroxy radicals and fundamentally lightening the burden of the main antioxidant and the auxiliary antioxidant; on the other hand, the advantages of the traditional antioxidant are kept, and the cost is reduced.
In conclusion, the antioxidant of the tetraphenol acrylate as the processing aid of the ABS resin has larger molecular weight, more stable state and stronger intramolecular hydrogen bonds, and has stronger synergistic effect when being compounded with other antioxidants; the composite processing aid disclosed by the invention can enhance the oxidation resistance of the ABS resin in a processing state, and can effectively improve the performances of the ABS resin such as yellow index and the like.
Detailed Description
The following examples illustrate the invention in detail: the present example is carried out on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following examples, and the experimental methods without specific conditions noted in the following examples are generally performed according to conventional conditions.
The processing aid for the ABS resin 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 tetra (4-hydroxyphenyl) methane, acrylic acid and halogenating agent is 1.25-1.5; the molar ratio of the halogenating agent to the catalyst is 1.
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, in the preparation method of the ABS resin processing aid, the tetraphenol acrylate is a product prepared by dissolving tetra (4-hydroxyphenyl) methane, acrylic acid and a halogenating agent in an organic solvent and performing one-step method under the action of a catalyst;
further, the reaction formula of the esterification reaction is:
the ABS resin composite processing aid provided by the invention comprises the following components:
10-30wt% of tetraphenol monoacrylate antioxidant,
20-40wt%, preferably 20-35wt%,
10-30wt%, preferably 20-30wt%,
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 antioxidant is antioxidant 168 and/or antioxidant 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% by mass based on the total mass of the ABS resin.
Example 1 Synthesis of Tetraphenol monoacrylate intramolecular multifunctional auxiliary
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 sequentially placed in a four-neck flask (500 ml) with a stirrer, a thermometer and a reflux condenser, the temperature is raised to 75 ℃ by stirring, 61.5g of phosphorus oxychloride is added dropwise (after the dropwise addition is completed within 0.6mol of 35min), and the temperature is kept for 2h. After the reaction, the obtained organic layer was separated as a reaction product and analyzed by liquid chromatography. Elution was performed with octafluorotoluene and the organic phases were combined. The octafluorotoluene was distilled off under reduced pressure, the remaining organic phase was recrystallized and filtered off with suction to give 71.8g of a white product in a yield of 91% by weight.
EXAMPLE 2 Synthesis of Tetraphenol monoacrylate intramolecular multifunctional auxiliary
61.5g (0.16 mol) of tetra (4-hydroxyphenyl) methane, 17.29g (0.24 mol) of acrylic acid, 16.19g (0.16 mol) of triethylamine and 150ml of octafluorotoluene are sequentially placed in a four-neck flask (500 ml) with a stirrer, a thermometer and a reflux condenser, the temperature is raised to 85 ℃ by stirring, 41.2g of phosphorus oxychloride is started to be dropwise added (the dropwise addition is completed within 35min of 0.4 mol), and the temperature is kept for 2.5h. After the reaction, the obtained organic layer was separated as a reaction product and analyzed by liquid chromatography. Eluting with octafluorotoluene, and combining the organic phases. The octafluorotoluene was distilled off under reduced pressure, and the remaining organic phase was recrystallized and filtered under suction to give 69.43g of a white product in 88% yield.
EXAMPLE 3 Synthesis of Tetraphenol monoacrylate intramolecular multifunctional auxiliary
61.5g (0.16 mol) of tetra (4-hydroxyphenyl) methane, 14.99g (0.21 mol) of acrylic acid, 16.19g (0.16 mol) of triethylamine and 150ml of octafluorotoluene are sequentially placed in a four-neck flask (500 ml) with a stirrer, a thermometer and a reflux condenser, the temperature is raised to 80 ℃ by stirring, 16.4g (the dropwise addition is completed within 0.45mol 35min) of phosphorus oxychloride is started to be dropwise added, and the temperature is kept for 2h. After the reaction was completed, the resultant organic layer was separated as a reaction product and analyzed by liquid chromatography. Eluting with octafluorotoluene, and combining the organic phases. The octafluorotoluene was distilled off under reduced pressure, the remaining organic phase was recrystallized and filtered with suction to give 70.9g of a white product with a yield of 90% by weight.
EXAMPLE 4 preparation of a Tetraphenol monoacrylate-containing composite auxiliary
20g of the tetraphenol monoacrylate prepared in example 1, 1010 20g of antioxidant, 168 40g of antioxidant and 20g of calcium stearate are weighed and uniformly mixed to prepare the composite additive 1.
EXAMPLE 5 preparation of a Tetraphenol monoacrylate-containing composite auxiliary
20g of the tetraphenol monoacrylate prepared in example 1, 20g of the antioxidant 3114, 168 40g of the antioxidant and 20g of magnesium stearate are weighed and mixed uniformly to prepare the composite auxiliary agent 2.
EXAMPLE 6 preparation of a Tetraphenol monoacrylate-containing composite auxiliary
Weighing 10g of the tetraphenol monoacrylate prepared in the embodiment 1, and uniformly mixing 1010 g of antioxidant, 626 30g of antioxidant and 30g of zinc stearate to prepare the composite auxiliary agent 3.
EXAMPLE 7 preparation of a Tetraphenol monoacrylate-containing composite auxiliary
30g of the tetraphenol monoacrylate prepared in the embodiment 1 is weighed, and uniformly mixed with 3114 g of the antioxidant, 168 20g of the antioxidant and 20g of zinc stearate to prepare the composite additive 4.
EXAMPLE 8 preparation of a Compound adjuvant containing Tetraphenol monoacrylate
25g of the tetraphenol monoacrylate prepared in the embodiment 1 is weighed, and 1010 g of the antioxidant, 168 20g of the antioxidant and 30g of the calcium stearate are uniformly mixed to prepare the composite auxiliary agent 5.
Comparative example 1 preparation of a Compound adjuvant containing bisphenol monoacrylate
Weighing 30g of bisphenol monoacrylate antioxidant, 1076 30g of antioxidant, 168 20g of antioxidant and 20g of calcium stearate, and uniformly mixing the four to prepare the bisphenol monoacrylate antioxidant composite additive, wherein the obtained product is marked as a comparative composite additive 1.
Comparative experiment 1:
weighing 25g of ABS powder and 75g of SAN powder, adding 1-5 of 0.3g of equivalent composite additive, mixing uniformly, and feeding into a feed inlet of a pre-heated (the pre-heating temperature is 210 ℃) mixing and granulating device for processing and granulating. Then according to GB 19466 oxidation induction period method for measuring thermal stability of plastic raw materials, differential Scanning Calorimetry (DSC) is used for evaluating the oxidation induction period of ABS resin at 160 ℃, and according to HG/T3862-2006 test method for yellow index of plastic, the evaluation result is shown in Table 1.
Wherein, the compound additive 6 is only the compound additive 1 is adjusted to be 0.4g according to the method, and the compound additive 7 is only the compound additive 1 is adjusted to be 0.55 according to the method;
wherein, the comparative sample 1 is obtained by replacing the composite additive 1 with a tetraphenol monoacrylate antioxidant according to the above method, the comparative sample 2 is obtained by replacing the composite additive 1 with a bisphenol monoacrylate antioxidant according to the above method, and the comparative sample 3 is obtained by replacing the composite additive 1 with the comparative composite additive 1 according to the above method.
TABLE 1 ABS resin Oxidation Induction phase Performance test
As can be seen from comparison of the comparative sample 1 and the comparative sample 2, the antioxidant performance of the tetra-phenol acrylate antioxidant serving as the ABS resin processing aid provided by the invention is superior to that of the existing bisphenol mono-acrylate antioxidant when the antioxidant is used alone.
As can be seen from the comparison of the composite additives 1 to 7 and the comparison sample 3, when the tetraphenol acrylate antioxidant serving as the ABS resin processing additive provided by the invention is compounded with other antioxidants (particularly 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 antioxidant performance.
From the above, the antioxidant of the tetraphenol acrylate as the processing aid of the ABS resin provided by the invention has the advantages that the intramolecular not only has the trimolecular phenolic hydroxyl similar to that of the antioxidant 1010, but also has the acrylic acid group with double bonds, so that the intramolecular hydrogen bond is enhanced. After the macromolecular free radical is captured by the acrylic acid group, the intramolecular hydrogen bond can be more quickly transferred to form stable phenoxy free radical. And because the antioxidant is of a branched structure, the physical property is stable, and the molecular weight is large, the extraction resistance and the migration resistance are improved.
According to the preparation method of the ABS resin processing aid, tetra (4-hydroxyphenyl) methane and acrylic acid are subjected to esterification reaction in an octafluorotoluene solvent to obtain the tetraphenol acrylate antioxidant with a relatively large molecular weight.
The invention provides an ABS resin composite processing aid, wherein a tetraphenol acrylate antioxidant is compounded with other antioxidants (particularly hindered phenol antioxidants and phosphite antioxidants) 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 defense line in advance, reducing the number of the subsequent generated peroxy radicals and fundamentally lightening the burden of the main antioxidant and the auxiliary antioxidant; on the other hand, the advantages of the traditional antioxidant are kept, and the cost is reduced.
In conclusion, the antioxidant of the tetraphenol acrylate as the processing aid of the ABS resin has larger molecular weight, more stable state and stronger intramolecular hydrogen bonds, and has stronger synergistic effect when being compounded with other antioxidants; the composite processing aid disclosed by the invention can enhance the oxidation resistance of the ABS resin in a processing state, and can effectively improve the performances of the ABS resin such as yellow index and the like.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention be considered as within the following claims.
Claims (11)
1. The ABS resin processing aid is characterized in that the processing aid is a tetraphenol monoacrylate antioxidant.
2. The ABS resin processing aid according to claim 1, wherein the tetraphenol monoacrylate antioxidant has a structure represented by formula I:
3. a method for preparing the ABS resin processing aid according to any one of claims 1-2, 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 tetra (4-hydroxyphenyl) methane, acrylic acid and halogenating agent is 1.25-1.5; the molar ratio of the halogenating agent to the catalyst is 1.
4. The method of claim 3, wherein the halogenating agent is phosphorus oxychloride and the catalyst is triethylamine.
5. The method of claim 3, wherein the organic solvent is one of octafluorotoluene, n-heptane and toluene.
6. The method for preparing an ABS resin processing aid according to claim 3, wherein 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%.
7. The ABS resin composite processing aid is characterized by comprising the following components:
10-30wt% of tetraphenol monoacrylate antioxidant,
20-40wt%, preferably 20-35wt%,
10-30wt%, preferably 20-30wt%,
20-30wt% of stearate.
8. The ABS resin composite processing aid according to claim 7, wherein the primary antioxidant is antioxidant 3114 and/or antioxidant 1010.
9. The ABS resin composite processing aid according to claim 7, wherein the auxiliary antioxidant is antioxidant 168 and/or antioxidant 626.
10. The ABS resin composite processing aid of claim 7 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 7, wherein the addition amount of the composite processing aid is 0.3-0.55% of the total mass of the ABS resin.
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