CN113736141A - Efficient ultraviolet-resistant antimony mercaptide composite heat stabilizer - Google Patents
Efficient ultraviolet-resistant antimony mercaptide composite heat stabilizer Download PDFInfo
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- CN113736141A CN113736141A CN202111027656.9A CN202111027656A CN113736141A CN 113736141 A CN113736141 A CN 113736141A CN 202111027656 A CN202111027656 A CN 202111027656A CN 113736141 A CN113736141 A CN 113736141A
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- antimony
- ultraviolet
- heat stabilizer
- composite heat
- isooctyl thioglycolate
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- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 45
- 229910052787 antimony Inorganic materials 0.000 title claims abstract description 41
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- -1 antimony penta- (isooctyl thioglycolate) Chemical compound 0.000 claims abstract description 18
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 230000002745 absorbent Effects 0.000 claims abstract description 7
- 239000002250 absorbent Substances 0.000 claims abstract description 7
- JCPWCCYHRVGYMG-UHFFFAOYSA-K antimony(3+) 8-methyl-2-sulfanylnonanoate Chemical compound [Sb+3].CC(C)CCCCCC(S)C([O-])=O.CC(C)CCCCCC(S)C([O-])=O.CC(C)CCCCCC(S)C([O-])=O JCPWCCYHRVGYMG-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000004014 plasticizer Substances 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 15
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 14
- 229910019142 PO4 Inorganic materials 0.000 claims description 10
- 239000010452 phosphate Substances 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 9
- OATORLCCIQBWBF-UHFFFAOYSA-K 6-methylheptyl 2-bis[[2-(6-methylheptoxy)-2-oxoethyl]sulfanyl]stibanylsulfanylacetate Chemical compound [Sb+3].CC(C)CCCCCOC(=O)C[S-].CC(C)CCCCCOC(=O)C[S-].CC(C)CCCCCOC(=O)C[S-] OATORLCCIQBWBF-UHFFFAOYSA-K 0.000 claims description 8
- IUNVCWLKOOCPIT-UHFFFAOYSA-N 6-methylheptylsulfanyl 2-hydroxyacetate Chemical compound CC(C)CCCCCSOC(=O)CO IUNVCWLKOOCPIT-UHFFFAOYSA-N 0.000 claims description 8
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 8
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007810 chemical reaction solvent Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000004821 distillation Methods 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 238000002156 mixing Methods 0.000 claims description 5
- 235000012424 soybean oil Nutrition 0.000 claims description 5
- 239000003549 soybean oil Substances 0.000 claims description 5
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- ALSTYHKOOCGGFT-KTKRTIGZSA-N (9Z)-octadecen-1-ol Chemical compound CCCCCCCC\C=C/CCCCCCCCO ALSTYHKOOCGGFT-KTKRTIGZSA-N 0.000 claims description 4
- YBGZDTIWKVFICR-JLHYYAGUSA-N Octyl 4-methoxycinnamic acid Chemical compound CCCCC(CC)COC(=O)\C=C\C1=CC=C(OC)C=C1 YBGZDTIWKVFICR-JLHYYAGUSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- XNEFYCZVKIDDMS-UHFFFAOYSA-N avobenzone Chemical compound C1=CC(OC)=CC=C1C(=O)CC(=O)C1=CC=C(C(C)(C)C)C=C1 XNEFYCZVKIDDMS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 229960001679 octinoxate Drugs 0.000 claims description 4
- 229940055577 oleyl alcohol Drugs 0.000 claims description 4
- XMLQWXUVTXCDDL-UHFFFAOYSA-N oleyl alcohol Natural products CCCCCCC=CCCCCCCCCCCO XMLQWXUVTXCDDL-UHFFFAOYSA-N 0.000 claims description 4
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 4
- 239000000244 polyoxyethylene sorbitan monooleate Substances 0.000 claims description 4
- 229920000053 polysorbate 80 Polymers 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- URBFWIOUKUBOAS-UHFFFAOYSA-N 1,1-bis(2,4-ditert-butylphenyl)-2,2-bis(hydroxymethyl)propane-1,3-diol phosphono dihydrogen phosphate Chemical compound OP(O)(=O)OP(=O)(O)O.C(C)(C)(C)C1=C(C=CC(=C1)C(C)(C)C)C(O)(C(CO)(CO)CO)C1=C(C=C(C=C1)C(C)(C)C)C(C)(C)C URBFWIOUKUBOAS-UHFFFAOYSA-N 0.000 claims description 2
- AIBRSVLEQRWAEG-UHFFFAOYSA-N 3,9-bis(2,4-ditert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP1OCC2(COP(OC=3C(=CC(=CC=3)C(C)(C)C)C(C)(C)C)OC2)CO1 AIBRSVLEQRWAEG-UHFFFAOYSA-N 0.000 claims description 2
- 229910003076 TiO2-Al2O3 Inorganic materials 0.000 claims description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 238000002845 discoloration Methods 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 14
- 229920000915 polyvinyl chloride Polymers 0.000 description 13
- 238000001816 cooling Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004040 coloring Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 230000006750 UV protection Effects 0.000 description 3
- CSHCPECZJIEGJF-UHFFFAOYSA-N methyltin Chemical compound [Sn]C CSHCPECZJIEGJF-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229940087291 tridecyl alcohol Drugs 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
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- 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
- C08K5/0091—Complexes with metal-heteroatom-bonds
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/132—Phenols containing keto groups, e.g. benzophenones
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention discloses a high-efficiency anti-ultraviolet antimony mercaptide composite heat stabilizer, and particularly relates to the technical field of PVC modification, wherein the high-efficiency anti-ultraviolet antimony mercaptide composite heat stabilizer comprises the following components in percentage by weight: 45-90% of antimony tri- (isooctyl thioglycolate), 0-55% of antimony penta- (isooctyl thioglycolate), 0.5-1.5% of ultraviolet absorbent, 1-10% of anti-precipitation agent, 2-6% of plasticizer and 1-2% of solubilizer. The high-efficiency ultraviolet-resistant antimony mercaptide composite heat stabilizer provided by the invention has the advantages of no toxicity, low price and difficult discoloration.
Description
Technical Field
The invention relates to the technical field of PVC modification, and particularly relates to a high-efficiency ultraviolet-resistant antimony mercaptide composite heat stabilizer.
Background
Polyvinyl chloride (PVC) resin is unstable in structure and is easily degraded in processing and molding. Degradation leads to a gradual darkening of the material and a loss of mechanical properties, so that heat stabilizers have to be used during its processing.
Among many heat stabilizers, heavy metal salt heat stabilizers such as lead and cadmium are effective in inhibiting the degradation of PVC, but have high toxicity and have a great influence on the environment and human health, and their use has been gradually prohibited. The current common organic tin heat stabilizer is nontoxic, has excellent initial coloring and heat stability, but is expensive and has higher use cost. Meanwhile, antimony mercaptide is a novel PVC heat stabilizer, has the advantages of good initial coloring and long-acting heat stability, low price, no toxicity and the like, and is a good substitute of the prior expensive organic tin heat stabilizer. However, the currently used organic antimony heat stabilizer has the problems of poor storage stability, poor ultraviolet light resistance and the like, so that PVC products added with the organic antimony heat stabilizer are prone to discoloring outdoors, and the large-scale use of the organic antimony heat stabilizer in the PVC industry is limited.
Therefore, the development of a nontoxic, low-cost and non-discoloring PVC heat stabilizer is an urgent problem to be solved by the technical staff.
Disclosure of Invention
The invention aims to provide a high-efficiency anti-ultraviolet antimony mercaptide composite heat stabilizer which has the advantages of no toxicity, low price and difficult discoloration.
In order to achieve the above purpose, the invention provides the following technical scheme:
the high-efficiency anti-ultraviolet antimony mercaptide composite heat stabilizer comprises the following components in percentage by weight: 45-90% of antimony tri- (isooctyl thioglycolate), 0-55% of antimony penta- (isooctyl thioglycolate), 0.5-1.5% of ultraviolet absorbent, 1-10% of anti-precipitation agent, 2-6% of plasticizer and 1-2% of solubilizer.
Wherein the ultraviolet absorbent is any one selected from 2-hydroxy-4-n-octyloxybenzophenone, dibenzoylmethane, 1- [4- (1, 1-dimethylethyl) phenyl ] -3- (4-methoxyphenyl) -1, 3-propanedione, ethylhexyl methoxycinnamate, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphate, or is selected from: any one of a mixture of 2-hydroxy-4-n-octyloxybenzophenone and dibenzoylmethane in a mass ratio of 1:1, a mixture of 2-hydroxy-4-n-octyloxybenzophenone and 1- [4- (1, 1-dimethylethyl) phenyl ] -3- (4-methoxyphenyl) -1, 3-propanedione in a mass ratio of 1:1, a mixture of 2-hydroxy-4-n-octyloxybenzophenone and ethylhexyl methoxycinnamate in a mass ratio of 1:1, and a mixture of 2-hydroxy-4-n-octyloxybenzophenone and bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphate in a mass ratio of 1: 1;
the anti-precipitation agent is selected from any one of oleyl alcohol polyoxyethylene ether-3-phosphate, phenol and catechol, or is selected from the following components: any one of a mixture with the mass ratio of catechol to oleyl alcohol polyoxyethylene ether-3-phosphate being 1:1 and a mixture with the mass ratio of catechol to phenol being 1: 1;
the plasticizer is selected from any one of epoxidized soybean oil and dioctyl phthalate, or a mixture of the epoxidized soybean oil and the dioctyl phthalate in a mass ratio of 1: 1;
the solubilizer is selected from any one of polyoxyethylene sorbitan monooleate and tridecyl polyether-10-phosphate, or a mixture of the polyoxyethylene sorbitan monooleate and the tridecyl polyether-10-phosphate in a mass ratio of 1: 1.
The efficient anti-ultraviolet antimony mercaptide composite heat stabilizer takes tri- (isooctyl thioglycolate) antimony and penta- (isooctyl thioglycolate) antimony as main raw materials, and a proper amount of ultraviolet absorbent is added to improve the anti-ultraviolet performance of the antimony mercaptide heat stabilizer and a PVC product; adding a proper amount of anti-precipitation agent and solubilizer to improve the storage stability of the antimony mercaptide heat stabilizer; and the plasticizer is added to improve the processing performance of the PVC. The ultraviolet absorbent, the anti-precipitation agent, the solubilizer and the plasticizer are added into raw materials of the tri- (isooctyl thioglycolate) antimony and the penta- (isooctyl thioglycolate) antimony in a certain proportion, the obtained antimony mercaptide composite heat stabilizer has the synergistic effect of the components, the optimal initial coloring and long-term heat stability are achieved, the product does not turn black or turn white after being exposed for a long time, the transparency of the product is good, the product is not easy to turn yellow, the product can replace expensive methyl tin and be independently used for processing PVC transparent products, and the cost performance is greatly improved.
Preferably, the structural formula of the antimony tris- (isooctyl thioglycolate) is as shown in formula (1):
preferably, the preparation method of the antimony tris- (isooctyl thioglycolate) comprises the following steps:
uniformly mixing antimony trioxide and isooctyl thioglycolate according to the mass ratio of 1: 6.0-7.2, adding a catalyst A, reacting for 3-5 hours at the temperature of 60-120 ℃ in a reaction solvent, carrying out reduced pressure distillation and dehydration, and filtering to obtain the antimony tris- (isooctyl thioglycolate).
Preferably, the structural formula of antimony penta- (isooctyl thioglycolate) is as shown in formula (2):
preferably, the preparation method of the antimony penta- (isooctyl thioglycolate) comprises the following steps:
uniformly mixing antimony pentoxide and isooctyl thioglycolate in a mass ratio of 1: 10-12, adding a catalyst B, reacting for 3-5 hours at the temperature of 60-120 ℃ in a reaction solvent, carrying out reduced pressure distillation and dehydration, and filtering to obtain antimony penta- (isooctyl thioglycolate).
Preferably, both catalyst A and catalyst B are selected from SO4 2-/TiO2、SO4 2-/Al2O3、SO4 2-/TiO2-Al2O3And one of strong acid cation exchange resin and perfluoro sulfonic acid resin, with the addition amount of 5-10%.
Preferably, the reaction temperature is 80 ℃.
Preferably, the reaction solvent is selected from any one of benzene, toluene and water.
Preferably, the reaction solvent is selected from water.
In the technical scheme, the invention provides the following technical effects and advantages:
(1) compared with the existing antimony mercaptide heat stabilizer in the market at present, the composite antimony mercaptide obtained by the invention has greatly improved comprehensive performance and cost performance, excellent initial coloring and long-term heat stability, good ultraviolet resistance effect and storage stability, no blackening due to long-time solarization under sunlight and no precipitation after long-term placement, and the PVC processing product has high transparency and good yellowing resistance effect, and solves the problems of poor storage stability, poor ultraviolet resistance and the like of the traditional antimony mercaptide heat stabilizer.
(2) The antimony mercaptide composite heat stabilizer obtained by the invention has the initial coloring and long-term heat stability equivalent to that of methyl tin, can replace expensive methyl tin to be independently used for processing PVC transparent products, and greatly improves the cost performance.
(3) The preparation process of the antimony mercaptide composite heat stabilizer is simple, environment-friendly, high in reaction yield, recyclable in catalyst, simple and easily available in raw materials, and suitable for industrial mass production.
Drawings
FIG. 1 is a schematic diagram of a dynamic thermal stability test of antimony mercaptide composite heat stabilizer;
FIG. 2 is a schematic diagram of an anti-ultraviolet performance test of an antimony mercaptide composite heat stabilizer.
Detailed Description
Example 1
A preparation method of a high-efficiency anti-ultraviolet antimony mercaptide composite heat stabilizer comprises the following steps:
in a 250mL three-necked flask equipped with a stirrer and a reflux condenser, 49.04g of isooctyl thioglycolate, 11.66g of antimony trioxide powder and 2.46g of SO were charged4 2-/TiO2And (3) reacting the catalyst for 3 hours at the temperature of 80 ℃, stopping stirring, heating, cooling, distilling under reduced pressure, and filtering to obtain light green antimony tris- (isooctyl thioglycolate) with the yield of 96%.
Example 2
A preparation method of a high-efficiency anti-ultraviolet antimony mercaptide composite heat stabilizer comprises the following steps:
into a 250mL three-necked flask equipped with a stirrer and a reflux condenser, 58.85g of isooctyl thioglycolate, 11.66g of antimony trioxide powder and 2.46g of SO were charged4 2-/TiO2The catalyst reacts for 3 hours at the temperature of 80 ℃, stirring and heating are stopped, cooling and reduced pressure distillation are carried out, and then filtration is carried out to obtain light green antimony tris- (isooctyl thioglycolate) with the yield of 97 percent.
A preparation method of a high-efficiency anti-ultraviolet antimony mercaptide composite heat stabilizer comprises the following steps:
in a 250mL three-necked flask equipped with a stirrer and a reflux condenser, 40.87g of isooctyl thioglycolate, 6.47g of antimony pentoxide powder and 2.0g of SO were charged4 2-/Al2O3The catalyst reacts for 3 hours at the temperature of 80 ℃, stirring and heating are stopped, cooling and reduced pressure distillation are carried out, and then filtration is carried out to obtain light green antimony penta- (isooctyl thioglycolate) with the yield of 97 percent.
Example 4
A preparation method of a high-efficiency anti-ultraviolet antimony mercaptide composite heat stabilizer comprises the following steps:
in a 250mL three-necked flask equipped with a stirrer and a reflux condenser, 49.04g of isooctyl thioglycolate, 6.47g of antimony pentoxide powder and 2.0g of SO were charged4 2-/Al2O3The catalyst reacts for 3 hours at the temperature of 80 ℃, stirring and heating are stopped, cooling and reduced pressure distillation are carried out, and then filtration is carried out to obtain light green antimony penta- (isooctyl thioglycolate) with the yield of 98 percent.
Case for compounding product
Case 1: and (2) adding 10g of the synthesized tri- (isooctyl thioglycolate) antimony into a 250mL three-neck flask provided with a stirrer and a reflux condenser device, sequentially and respectively adding 0.1g of 2-hydroxy-4-n-octoxy benzophenone, 0.1g of catechol, 0.2g of dioctyl phthalate and 0.1g of tridecyl polyether-10-phosphate, heating to 50-60 ℃ after the addition, stirring for 30 minutes, and cooling to obtain the antimony mercaptide composite heat stabilizer.
Case 2: 9g of the synthesized tri- (isooctyl thioglycolate) antimony and 1g of penta- (isooctyl thioglycolate) antimony are added into a 250mL three-neck flask provided with a stirrer and a reflux condenser device, 0.1g of dibenzoylmethane, 0.1g of phenol, 0.2g of epoxidized soybean oil and 0.1g of tridecyl alcohol polyether-10-phosphate are sequentially added respectively, the temperature is raised to 50-60 ℃ after the addition is finished, the stirring is carried out for 30 minutes, and the antimony mercaptide composite heat stabilizer is obtained after the cooling.
Test example 1
100g of PVC resin and 0.8g of the synthesized antimony mercaptide composite heat stabilizer are uniformly mixed and mixed on an open plasticator, the temperature is 195 +/-2 ℃, the rotor speed is 40r/min, the time from plasticizing to decomposing of the PVC is recorded, and the result shows that the mixing time is as long as 22 minutes, as shown in figure 1.
Test example 2
The antimony mercaptide composite heat stabilizer obtained by the invention and the existing antimony mercaptide product HTM2080 in the market are respectively put into a plastic bottle and are exposed to the sun, the blackening time of the product is recorded, and the ultraviolet resistance effect of the product is correspondingly achieved. The results of the study showed that exposure to the sun for 930 minutes did not turn black as shown in figure 2.
Claims (9)
1. The high-efficiency anti-ultraviolet antimony mercaptide composite heat stabilizer is characterized by comprising the following components in percentage by weight: 45-90% of antimony tri- (isooctyl thioglycolate), 0-55% of antimony penta- (isooctyl thioglycolate), 0.5-1.5% of ultraviolet absorbent, 1-10% of anti-precipitation agent, 2-6% of plasticizer and 1-2% of solubilizer;
wherein the ultraviolet absorbent is any one selected from 2-hydroxy-4-n-octyloxybenzophenone, dibenzoylmethane, 1- [4- (1, 1-dimethylethyl) phenyl ] -3- (4-methoxyphenyl) -1, 3-propanedione, ethylhexyl methoxycinnamate, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphate, or is selected from: any one of a mixture of 2-hydroxy-4-n-octyloxybenzophenone and dibenzoylmethane in a mass ratio of 1:1, a mixture of 2-hydroxy-4-n-octyloxybenzophenone and 1- [4- (1, 1-dimethylethyl) phenyl ] -3- (4-methoxyphenyl) -1, 3-propanedione in a mass ratio of 1:1, a mixture of 2-hydroxy-4-n-octyloxybenzophenone and ethylhexyl methoxycinnamate in a mass ratio of 1:1, and a mixture of 2-hydroxy-4-n-octyloxybenzophenone and bis (2, 4-di-t-butylphenyl) pentaerythritol diphosphate in a mass ratio of 1: 1;
the anti-precipitation agent is selected from any one of oleyl alcohol polyoxyethylene ether-3-phosphate, phenol and catechol, or is selected from the following components: any one of a mixture with the mass ratio of catechol to oleyl alcohol polyoxyethylene ether-3-phosphate being 1:1 and a mixture with the mass ratio of catechol to phenol being 1: 1;
the plasticizer is selected from any one of epoxidized soybean oil and dioctyl phthalate, or a mixture of the epoxidized soybean oil and the dioctyl phthalate in a mass ratio of 1: 1;
the solubilizer is selected from any one of polyoxyethylene sorbitan monooleate and tridecyl polyether-10-phosphate, or a mixture of the polyoxyethylene sorbitan monooleate and the tridecyl polyether-10-phosphate in a mass ratio of 1: 1.
2. The efficient anti-ultraviolet antimony mercaptide composite heat stabilizer of claim 1, wherein the structural formula of antimony tris- (isooctyl thioglycolate) is shown in formula (1):
3. the efficient anti-ultraviolet antimony mercaptide composite heat stabilizer of claim 2, wherein the preparation method of the antimony tris- (isooctyl thioglycolate) comprises the following steps:
uniformly mixing antimony trioxide and isooctyl thioglycolate according to the mass ratio of 1: 6.0-7.2, adding a catalyst A, reacting for 3-5 hours at the temperature of 60-120 ℃ in a reaction solvent, carrying out reduced pressure distillation and dehydration, and filtering to obtain the antimony tris- (isooctyl thioglycolate).
4. The efficient anti-ultraviolet antimony mercaptide composite heat stabilizer as claimed in claim 1, wherein the structural formula of antimony penta- (isooctyl thioglycolate) is as shown in formula (2):
5. the efficient anti-ultraviolet antimony mercaptide composite heat stabilizer of claim 4, wherein the preparation method of antimony penta- (isooctyl thioglycolate) comprises the following steps:
uniformly mixing antimony pentoxide and isooctyl thioglycolate in a mass ratio of 1: 10-12, adding a catalyst B, reacting for 3-5 hours at the temperature of 60-120 ℃ in a reaction solvent, carrying out reduced pressure distillation and dehydration, and filtering to obtain antimony penta- (isooctyl thioglycolate).
6. The high-efficiency anti-ultraviolet antimony mercaptide composite heat stabilizer as claimed in any one of claims 3 and 5, wherein catalyst A and catalyst B are selected from SO4 2-/TiO2、SO4 2-/Al2O3、SO4 2-/TiO2-Al2O3The catalyst A and the catalyst B are added in an amount of 5-10%.
7. The high-efficiency anti-ultraviolet antimony mercaptide composite heat stabilizer as claimed in any one of claims 3 and 5, wherein the reaction temperature is 80 ℃.
8. The high-efficiency anti-ultraviolet antimony mercaptide composite heat stabilizer according to any one of claims 3 and 5, wherein the reaction solvent is any one selected from benzene, toluene and water.
9. The high-efficiency anti-ultraviolet antimony mercaptide composite heat stabilizer as claimed in claim 8, wherein the reaction solvent is selected from water.
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| US4231895A (en) * | 1979-01-02 | 1980-11-04 | M & T Chemicals Inc. | Synergistic heat stabilizer compositions containing an antimony or a bismuth compound |
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| CN106083671A (en) * | 2016-06-17 | 2016-11-09 | 浙江海普顿新材料股份有限公司 | The method that pre-emulsification prepares high antimony content mercaptans type without catalyst |
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