CN110655680B - Mixed anion zinc monomer, and composition and application thereof - Google Patents
Mixed anion zinc monomer, and composition and application thereof Download PDFInfo
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 45
- 239000011701 zinc Substances 0.000 title claims abstract description 45
- 239000000203 mixture Substances 0.000 title claims abstract description 33
- 239000000178 monomer Substances 0.000 title claims abstract description 33
- 150000001450 anions Chemical class 0.000 title abstract description 6
- -1 mercaptopropionic acid fatty alcohol ester Chemical class 0.000 claims abstract description 27
- 125000000129 anionic group Chemical group 0.000 claims abstract description 21
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 14
- DKIDEFUBRARXTE-UHFFFAOYSA-N 3-mercaptopropanoic acid Chemical compound OC(=O)CCS DKIDEFUBRARXTE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000021355 Stearic acid Nutrition 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
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008117 stearic acid Substances 0.000 claims abstract description 7
- 239000011787 zinc oxide Substances 0.000 claims abstract description 7
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 5
- 239000012760 heat stabilizer Substances 0.000 claims description 13
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 12
- 229960001545 hydrotalcite Drugs 0.000 claims description 12
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 8
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 8
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 5
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 claims description 5
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 5
- LQZZUXJYWNFBMV-UHFFFAOYSA-N dodecan-1-ol Chemical compound CCCCCCCCCCCCO LQZZUXJYWNFBMV-UHFFFAOYSA-N 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical group [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 3
- NZZIMKJIVMHWJC-UHFFFAOYSA-N dibenzoylmethane Chemical compound C=1C=CC=CC=1C(=O)CC(=O)C1=CC=CC=C1 NZZIMKJIVMHWJC-UHFFFAOYSA-N 0.000 claims description 3
- CNUJLMSKURPSHE-UHFFFAOYSA-N trioctadecyl phosphite Chemical compound CCCCCCCCCCCCCCCCCCOP(OCCCCCCCCCCCCCCCCCC)OCCCCCCCCCCCCCCCCCC CNUJLMSKURPSHE-UHFFFAOYSA-N 0.000 claims description 3
- ZTOTXIJTXLDCFH-UHFFFAOYSA-N O(P(OCCCCCCCCCCCCCCCCCC)OP(O)O)CCCCCCCCCCCCCCCCCC.OCC(CO)(CO)CO Chemical compound O(P(OCCCCCCCCCCCCCCCCCC)OP(O)O)CCCCCCCCCCCCCCCCCC.OCC(CO)(CO)CO ZTOTXIJTXLDCFH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229960000541 cetyl alcohol Drugs 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000003112 inhibitor Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000007127 saponification reaction Methods 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- VLILFBZIVHDKIJ-UHFFFAOYSA-N 1-(2-ethylphenyl)ethanone Chemical compound CCC1=CC=CC=C1C(C)=O VLILFBZIVHDKIJ-UHFFFAOYSA-N 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical group SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 150000002978 peroxides Chemical class 0.000 abstract description 3
- 230000003064 anti-oxidating effect Effects 0.000 abstract description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 25
- 229920000915 polyvinyl chloride Polymers 0.000 description 24
- 239000003381 stabilizer Substances 0.000 description 7
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Natural products CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- PMNLUUOXGOOLSP-UHFFFAOYSA-M 2-sulfanylpropanoate Chemical compound CC(S)C([O-])=O PMNLUUOXGOOLSP-UHFFFAOYSA-M 0.000 description 2
- GGQOYCFZZZEZMA-UHFFFAOYSA-N 4-ethyl-1-phenyloctane-1,3-dione Chemical compound CCCCC(CC)C(=O)CC(=O)C1=CC=CC=C1 GGQOYCFZZZEZMA-UHFFFAOYSA-N 0.000 description 2
- RQWDXNAIEYQSPX-UHFFFAOYSA-N C(CCCCCCCCCCCCCCCCC)(=O)O.C(CCCCCCCCCCCCCCCCC)(=O)O.OP(O)OP(O)O.OCC(CO)(CO)CO Chemical compound C(CCCCCCCCCCCCCCCCC)(=O)O.C(CCCCCCCCCCCCCCCCC)(=O)O.OP(O)OP(O)O.OCC(CO)(CO)CO RQWDXNAIEYQSPX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000007613 environmental 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
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001934 delay Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/37—Thiols
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a mixed anion zinc monomer, a composition and application thereof. The invention utilizes esterification reaction to connect carboxyl in mercaptopropionic acid molecules with hydroxyl in fatty alcohol to form mercaptopropionic acid fatty alcohol ester, and then the mercaptopropionic acid fatty alcohol ester is melted and mixed with stearic acid and reacts with zinc oxide to obtain the zinc with a mixed anion structure. The zinc monomer compound of the invention introduces a mercaptan structure which can effectively decompose peroxide and has good antioxidation; the composition comprising the mixed anionic zinc monomer, which is added to PVC, can significantly improve the thermal stability, self-lubricity and transparency of PVC.
Description
Technical Field
The invention relates to a stabilizer for transparent PVC, in particular to a mixed anionic zinc monomer for transparent PVC, a composition and application thereof.
Background
Polyvinyl chloride (PVC) is one of five common plastics, and its global production is second only to polyethylene four. Compared with other general-purpose resins, the resin has poor inherent thermal stability, and the product is easy to deepen color and reduce performance during the processing and forming process, so that the application and development of the resin are limited, and a proper stabilizer is added during the processing process. Currently, lead salts, organotin compounds, metallic soaps and rare earth compounds are widely used as PVC heat stabilizers. In the face of increasingly strict environmental regulations, research and development of novel environmental-friendly PVC heat stabilizers have become a necessary trend.
The heat stabilizer used in the earliest process of processing polyvinyl chloride products is a lead salt heat stabilizer, but the lead salt heat stabilizer cannot be used for producing transparent products, and lead salt is toxic and does not meet the requirement of environmental protection. The calcium-zinc heat stabilizer is a typical representative of nontoxic additives in the polyvinyl chloride industry, and compared with an organic tin stabilizer, the calcium-zinc heat stabilizer is tasteless, has lower cost and the like and has the remarkable advantages of no odor. The research of the calcium-zinc heat stabilizer focuses on improving the early-stage coloring performance and the later-stage stability of PVC.
There is still little research on calcium zinc stabilizers for clear PVC.
Disclosure of Invention
The invention aims to provide a mixed anionic zinc monomer, a composition and an application thereof, wherein the mixed anionic zinc monomer is introduced into a mercaptan (-Zn-S-) structure which can effectively decompose peroxide so as to improve the oxidation resistance; the composition comprising the mixed anionic zinc monomer is added to PVC to significantly improve the thermal stability, self-lubricity and transparency of PVC.
Therefore, the invention adopts a technical scheme that: a mixed anionic zinc monomer prepared by the process of:
1) esterification reaction: with mercaptopropionic acid and C8～C22Fatty alcohol is taken as a raw material, sodium bisulfate is taken as a catalyst, the reaction is continued for 2.5 to 3.5 hours at the temperature of 105-115 ℃ and under the condition that the vacuum degree is between minus 0.06 and minus 0.09MPa, the generated water is removed, the sodium bisulfate is removed by water washing, and the fatty alcohol mercaptopropionate is obtained by dehydration;
2) metal saponification reaction: adding a proper amount of stearic acid into the reactant obtained in the step 1), uniformly mixing, adding zinc oxide, heating to 105-115 ℃, reacting for 2.5-3.5 hours, dehydrating and drying after the reaction is finished to obtain the mixed anionic zinc monomer.
The invention firstly synthesizes mercaptopropionate by esterification of mercaptopropionic acid and fatty alcohol, and then the mercaptopropionate is mixed with stearic acid and then reacts with zinc oxide to prepare the mixed anionic zinc monomer.
Further, said C8～C22The fatty alcohol is lauryl alcohol or palmityl alcohol.
The other technical scheme adopted by the invention is as follows: a composition containing the mixed anionic zinc monomer comprises the following components in parts by weight:
further, the zinc burning inhibitor is any one or a mixture of dibenzoyl methane, oleoyl benzoyl methane and 2-ethyl hexanoyl benzoyl methane.
Further, the phosphite ester is any one or a mixture of more of trioctadecyl phosphite, pentaerythritol distearyl diphosphite and tris (2, 4-di-tert-butyl) phenyl phosphite.
Further, the antioxidant is any one or a mixture of more of tetra [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 2, 6-di-tert-butyl-p-cresol and didodecyl thiodipropionate.
Further, the hydrotalcite is magnesium-aluminum hydrotalcite, magnesium-aluminum-zinc hydrotalcite or magnesium-aluminum-calcium-zinc hydrotalcite.
The mixed anionic zinc monomer and the composition thereof have white powder appearance.
The invention also adopts a technical scheme that: the composition is used as a heat stabilizer for transparent PVC, and the addition amount of the composition is 1-5g added to 100g of PVC.
The invention utilizes esterification reaction to connect carboxyl in mercaptopropionic acid molecules with hydroxyl in fatty alcohol to form mercaptopropionic acid fatty alcohol ester, then the mercaptopropionic acid fatty alcohol ester is melted and mixed with stearic acid and reacts with zinc oxide to obtain zinc with a mixed anion structure, and the zinc monomer and a traditional stabilizer form a composition. Compared with the traditional calcium-zinc stabilizer, the calcium-zinc stabilizer has the advantages that:
1. the mixed anion zinc compound has a longer carbon chain structure, so that the mixed anion zinc compound has better compatibility with PVC molecules, is beneficial to uniform dispersion of a heat stabilizer, and shows better transparency in the same addition part.
2. The mixed anion zinc compound has a longer carbon chain structure, so that the mixed anion zinc compound can show better lubricating effect in the PVC processing process, reduces the frictional heat generation among PVC particles and between PVC and processing equipment in the processing process, delays the degradation of PVC and is beneficial to improving the thermal stability of PVC.
3. The zinc monomer compound introduces a mercaptan (-Zn-S-) structure which can effectively decompose peroxide and has good antioxidation.
Detailed Description
The invention is further illustrated by the following examples, without restricting its scope.
Preparation of mono-and mixed anionic zinc monomer
Example 1
Putting 106g of mercaptopropionic acid, 186g of lauryl alcohol and 2g of sodium bisulfate into a reactor, stirring, heating to 112 ℃, continuously reacting for 3 hours under the condition that the vacuum degree is-0.06 MPa, removing generated water, washing with water to remove sodium bisulfate, and dehydrating to obtain 274g of mercaptopropionic acid lauryl alcohol; and mixing the reaction product with 284g of stearic acid for 30 minutes, adding 40g of zinc oxide, keeping the temperature of 105 ℃, reacting for 2.5 hours, dehydrating, and drying to obtain a No. 1 zinc monomer, wherein the zinc content is 5.1% by determination.
Example 2
Putting 106g of mercaptopropionic acid, 214g of palm alcohol and 2g of sodium bisulfate into a reactor, stirring, heating to 115 ℃, continuously reacting for 3 hours under the condition that the vacuum degree is-0.06 MPa, removing generated water, washing with water to remove the sodium bisulfate, and dehydrating to obtain 302g of mercaptopropionic acid lauryl alcohol; and mixing the reaction product with 284g of stearic acid for 30 minutes, adding 40g of zinc oxide, keeping the temperature of 105 ℃, reacting for 2.5 hours, dehydrating, and drying to obtain a No. 2 zinc monomer, wherein the zinc content is 4.9% by determination.
Preparation of composition containing mixed anionic zinc monomer
Example 3
A composition comprising mixed anionic zinc monomers, said composition being processed from the following components: 15g of No. 1 zinc monomer, 20g of trioctadecyl phosphite, 5g of antioxidant tetra [ methyl-beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 2g of dibenzoyl methane and 40g of magnesium aluminum hydrotalcite.
Example 4
A composition comprising mixed anionic zinc monomers, said composition being processed from the following components: 20g of No. 1 zinc monomer, 17g of pentaerythritol distearate diphosphite, 10g of antioxidant 2, 6-di-tert-butyl-p-cresol or didodecyl thiodipropionate, 3g of oleoyl benzoyl methane and 45g of magnesium-aluminum-zinc hydrotalcite.
Example 5
A composition comprising mixed anionic zinc monomers, said composition being processed from the following components: 18g of No. 2 zinc monomer, 20g of tris (2, 4-di-tert-butyl) phenyl phosphite, 12g of antioxidant didodecyl thiodipropionate or 2, 6-di-tert-butyl-p-cresol, 3g of 2-ethyl hexanoyl benzoyl methane and 50g of magnesium, aluminum, calcium and zinc hydrotalcite.
Example 6
A composition comprising mixed anionic zinc monomers, said composition being processed from the following components: 25g of No. 2 zinc monomer, 20g of pentaerythritol distearate diphosphite, 10g of antioxidant 2, 6-di-tert-butyl-p-cresol or didodecyl thiodipropionate, 3g of oleoyl benzoyl methane and 48g of magnesium-aluminum-zinc hydrotalcite.
Third, comparative experiment of thermal stability
Formulation (PHR): PVC (SG-7) (China petrochemicals-Qilu Ltd.): 100g, powder heat stabilizer: 2g, DOP (china petrochemicals-qilu gmbh): 30 g.
The mixed anionic zinc monomer composition prepared in the embodiment 3-6 is taken to prepare a PVC sample according to the formula, and a PVC transparent product is prepared according to the same formula by taking the commercially available powdery composite heat stabilizer white sand 104 and Baotai 695 respectively as a comparison.
The PVC samples were tested for zinc burn time and clarity as follows:
accurately weighing each component according to the PVC formula, uniformly mixing the materials by using an experimental mixer, mixing on an open type plastic mixing machine (Shanghai Hongyang machinery Co., Ltd.) at the temperature of 190 +/-2 ℃ for about 5min to prepare a sample piece with the thickness of about 1mm, cutting the prepared PVC sample piece into a sheet sample with the thickness of 1cm multiplied by 3cm, putting the sheet sample into an aging test box (401A, Shanghai brocade instrument and meter Co., Ltd.), drying at the temperature of 190 +/-2 ℃, taking the sheet every 10min, observing the color of the sheet sample and recording the yellow index.
Table 1: zinc burning time and light transmittance test
| Performance of | Zinc roasting time (min) | Light transmittance |
| Example 3 | 38 | 93 |
| Example 4 | 36 | 94 |
| Example 5 | 37 | 94 |
| Example 6 | 37 | 95 |
| Comparative example 1 (white sand 104) | 25 | 87 |
| Comparative example 2 (Baotai 695) | 27 | 86 |
The experimental data show that compared with the similar products sold in the market, the mixed anion zinc composition prepared by the invention has the advantages of obviously prolonged zinc burning time and better light transmittance.
Claims (8)
1. A mixed anionic zinc monomer, characterized in that it is prepared by the following process:
1) esterification reaction: with mercaptopropionic acid and C8～C22Fatty alcohol is taken as a raw material, sodium bisulfate is taken as a catalyst, the reaction is continued for 2.5 to 3.5 hours at the temperature of 105-115 ℃ and under the condition that the vacuum degree is between minus 0.06 and minus 0.09MPa, the generated water is removed, the sodium bisulfate is removed by water washing, and the fatty alcohol mercaptopropionate is obtained by dehydration;
the chemical equation for this reaction is as follows:
2) metal saponification reaction: adding a proper amount of stearic acid into the reactant obtained in the step 1), uniformly mixing, adding zinc oxide, heating to 105-115 ℃, reacting for 2.5-3.5 hours, dehydrating and drying after the reaction is finished to obtain a mixed anionic zinc monomer;
the chemical equation for this reaction is as follows:
2. a method as claimed in claim 1Mixed anionic zinc monomers, characterized in that C is8～C22The fatty alcohol is lauryl alcohol or palmityl alcohol.
3. A composition comprising the mixed anionic zinc monomer of claim 1 or 2, comprising the following components in parts by weight:
4. the composition according to claim 3, wherein the zinc burn inhibitor is any one or more of dibenzoylmethane, oleoylbenzoylmethane, and 2-ethylbenzoylmethane.
5. The composition of claim 3, wherein the phosphite is any one or more of trioctadecyl phosphite, pentaerythritol distearyl diphosphite, and phenyl tris (2, 4-di-tert-butyl) phosphite.
6. The composition of claim 3, wherein the antioxidant is any one or more of tetrakis [ methyl- β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol ester, 2, 6-di-tert-butyl-p-cresol, and didodecyl thiodipropionate.
7. The composition of claim 3, wherein the hydrotalcite is magnesium aluminum hydrotalcite, magnesium aluminum zinc hydrotalcite, or magnesium aluminum calcium zinc hydrotalcite.
8. Use of a composition according to any of claims 3 to 7 as a heat stabilizer for transparent PVC, in an amount of 1 to 5g per 100g of PVC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910991180.7A CN110655680B (en) | 2019-10-18 | 2019-10-18 | Mixed anion zinc monomer, and composition and application thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910991180.7A CN110655680B (en) | 2019-10-18 | 2019-10-18 | Mixed anion zinc monomer, and composition and application thereof |
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| Publication Number | Publication Date |
|---|---|
| CN110655680A CN110655680A (en) | 2020-01-07 |
| CN110655680B true CN110655680B (en) | 2021-07-13 |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103224675A (en) * | 2013-05-24 | 2013-07-31 | 河南正通化工有限公司 | Food-grade plastic PVC (polyvinyl chloride) heat stabilizer and preparation method thereof |
| CN105713316A (en) * | 2016-02-23 | 2016-06-29 | 东莞市尚诺新材料有限公司 | Transparent phenol-free pasty heat stabilizer and preparing method thereof |
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| WO2019151355A1 (en) * | 2018-02-02 | 2019-08-08 | 株式会社Adeka | Stabilizer composition, vinyl chloride resin composition containing same, and article molded therefrom |
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| US20070265378A1 (en) * | 2004-09-29 | 2007-11-15 | Kaneka Corporation | Polyvinyl Chloride Fiber Reduced in Initial Coloration |
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| CN103224675A (en) * | 2013-05-24 | 2013-07-31 | 河南正通化工有限公司 | Food-grade plastic PVC (polyvinyl chloride) heat stabilizer and preparation method thereof |
| CN105713316A (en) * | 2016-02-23 | 2016-06-29 | 东莞市尚诺新材料有限公司 | Transparent phenol-free pasty heat stabilizer and preparing method thereof |
| CN106188938A (en) * | 2016-07-08 | 2016-12-07 | 浙江海普顿新材料股份有限公司 | A kind of powder body zinc-base composite thermal stabilizer and preparation method |
| CN106316899A (en) * | 2016-08-17 | 2017-01-11 | 浙江海普顿新材料股份有限公司 | Thiosalicylic acid fatty alcohol ester barium and preparation method, composition and application thereof |
| WO2019151355A1 (en) * | 2018-02-02 | 2019-08-08 | 株式会社Adeka | Stabilizer composition, vinyl chloride resin composition containing same, and article molded therefrom |
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