NL2029765B1 - Synergistic heat stabilizer and use thereof in improving thermal stability of pvc - Google Patents
Synergistic heat stabilizer and use thereof in improving thermal stability of pvc Download PDFInfo
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- NL2029765B1 NL2029765B1 NL2029765A NL2029765A NL2029765B1 NL 2029765 B1 NL2029765 B1 NL 2029765B1 NL 2029765 A NL2029765 A NL 2029765A NL 2029765 A NL2029765 A NL 2029765A NL 2029765 B1 NL2029765 B1 NL 2029765B1
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- pvc
- heat stabilizer
- weight
- butyl titanate
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- 239000012760 heat stabilizer Substances 0.000 title claims abstract description 42
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 32
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 239000000344 soap Substances 0.000 claims abstract description 42
- 230000005855 radiation Effects 0.000 claims abstract description 36
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 32
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000000463 material Substances 0.000 claims abstract description 26
- 230000000087 stabilizing effect Effects 0.000 claims abstract description 9
- -1 cerium metals Chemical class 0.000 claims abstract description 7
- 239000007822 coupling agent Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims description 45
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical compound O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 claims description 32
- 239000003381 stabilizer Substances 0.000 claims description 19
- 239000002243 precursor Substances 0.000 claims description 18
- 238000005516 engineering process Methods 0.000 claims description 16
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- 239000000155 melt Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- BTVVNGIPFPKDHO-UHFFFAOYSA-K cerium(3+);octadecanoate Chemical compound [Ce+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O BTVVNGIPFPKDHO-UHFFFAOYSA-K 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 6
- 239000000758 substrate Substances 0.000 claims 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 46
- 239000002131 composite material Substances 0.000 abstract description 17
- 238000004132 cross linking Methods 0.000 abstract description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 96
- 239000004800 polyvinyl chloride Substances 0.000 description 96
- YAHBZWSDRFSFOO-UHFFFAOYSA-L dimethyltin(2+);2-(2-ethylhexoxy)-2-oxoethanethiolate Chemical compound CCCCC(CC)COC(=O)CS[Sn](C)(C)SCC(=O)OCC(CC)CCCC YAHBZWSDRFSFOO-UHFFFAOYSA-L 0.000 description 18
- 238000010438 heat treatment Methods 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 15
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 15
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 230000003247 decreasing effect Effects 0.000 description 13
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 12
- 229910052746 lanthanum Inorganic materials 0.000 description 9
- 230000006698 induction Effects 0.000 description 8
- 229910052725 zinc Inorganic materials 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 6
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000008116 calcium stearate Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 239000006084 composite stabilizer Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 2
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 2
- 235000013539 calcium stearate Nutrition 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000013068 control sample Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- RWXOJQGSZWUIEJ-UHFFFAOYSA-K lanthanum(3+);octadecanoate Chemical compound [La+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O RWXOJQGSZWUIEJ-UHFFFAOYSA-K 0.000 description 2
- 235000019359 magnesium stearate Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000761389 Copa Species 0.000 description 1
- 101000617550 Dictyostelium discoideum Presenilin-A Proteins 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000003287 bathing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- LUZSPGQEISANPO-UHFFFAOYSA-N butyltin Chemical compound CCCC[Sn] LUZSPGQEISANPO-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- ZMHZSHHZIKJFIR-UHFFFAOYSA-N octyltin Chemical compound CCCCCCCC[Sn] ZMHZSHHZIKJFIR-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920005906 polyester polyol Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
Classifications
-
- 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
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/057—Metal alcoholates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/203—Solid polymers with solid and/or liquid additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/223—Packed additives
-
- 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
-
- 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
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic 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
- C08K5/10—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
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin 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
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
- C08K5/58—Organo-tin compounds containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use 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; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention discloses a synergistic heat stabilizer and use thereof in improving thermal stability of PVC. The synergistic heat stabilizer takes organic tin, a cerium metal soap and butyl titanate as active components; and since crosslinking between a butyl titanate coupling agent and tin and cerium metals and PVC is enhanced after microwave radiation, the synergistic heat stabilizer can be used for preparing a novel PVC composite film material having a good heat stabilizing effect as well as potential resistance to microwave radiation.
Description
SYNERGISTIC HEAT STABILIZER AND USE THEREOF IN
IMPROVING THERMAL STABILITY OF PVC
The present invention belongs to the field of high polymer material processing aids, and particularly relates to a synergistic heat stabilizer and use thereof in improving the thermal stability of PVC.
With people's increasing environmental awareness, heat stabilizers of polyvinyl chloride films or products are already developing toward nontoxicity, a high efficiency, multiple functions, a good cost performance and degradability. The use of organic tin heat stabilizers keeps increasing to gradually replace lead-salt stabilizers. But common organic tin stabilizers are expensive and smelly and cannot meet the demand for a heat stabilizing effect. Therefore, the top priority is to adopt different components and different methods to improve the thermal stability of PVC, reduce the usage and cost of organic tin, and seek a synergistic effect and environmental degradability.
Microwaves are widely used in the fields of chemistry & chemical industry and materials, and generally have three functions: 1) the microwaves can increase temperature quickly since the heat conduction is different from that of traditional heating; 2) the microwaves have a specificity of promoting reaction conversion and selectivity; and 3) the microwaves can realize thermal degradation. The functions 1) and 3) are quite common. As for the function 2), a high selectivity and a good effect are closely related to a reactant composition. No reports are available on using microwaves to assist in preparation of a cerium metal soap and butyl titanate composite stabilizer for PVC.
In order to solve the problems of a high price and a relatively poor heat resistance of current methyl tin mercaptide, the present invention provides a synergistic heat stabilizer and use thereof in improving thermal stability of PVC. The present invention takes organic tin, a cerium metal soap and butyl titanate as active components; and since crosslinking between a butyl titanate coupling agent and tin and cerium metals and PVC is enhanced after microwave 1 radiation, the synergistic heat stabilizer can be used for preparing a novel PVC composite film material having a good heat stabilizing effect as well as potential resistance to microwave radiation.
Tetrabutyl titanate is colorless to light yellow oily liquid, with a relatively density of 0.966, a freezing point of -55°C, a flash point of 76.7°C and a boiling point of 310-314°C, and is an organic titanium compound which is used as a catalyst for a polycondensation reaction and a crosslinking reaction and is mainly applied to esterifying and transesterification reactions such as synthesis of polyester polyol; and the tetrabutyl titanate also can be used in a metal-plastic tackifier, a high-strength polyester paint modifier, a crosslinking agent and the like.
In the synergistic heat stabilizer of the present invention, organic tin is used as a primary heat stabilizer; and a butyl titanate modified cerium metal soap complex is used as an auxiliary stabilizer. The butyl titanate as a coupling agent has a notable synergistic stabilizing effect on the organic tin and the cerium metal soap, and can effectively improve the thermal stability of
PVC.
The synergistic heat stabilizer of the present invention includes the following components: 1.0-5.0 mass parts of the butyl titanate, 1.0-5.0 mass parts of the cerium metal soap and 0.1-1.0 mass part of the organic tin heat stabilizer.
Preferably, 1.0-5.0 mass parts of the butyl titanate, 1.0-5.0 mass parts of the cerium metal soap and 0.5 mass part of the organic tin heat stabilizer.
The cerium metal soap is cerium stearate.
The organic tin includes methyl tin mercaptide, octyl tin mercaptide, butyl tin mercaptide and dioctyl tin laurate.
A preparation method of the synergistic heat stabilizer of the present invention includes the following steps: mixing and dissolving 50 mass parts of DOTP, 1.0-5.0 mass parts of the butyl titanate, 1.0- 5.0 mass parts of the cerium metal soap and 0.1-1.0 mass part of the organic tin heat stabilizer by a microwave radiation technology; and then putting the mixture into a glass container, and starting a mixed microwave (17% of power output) radiation for 15 min in a microwave oven with a power of 700 w, to obtain a uniform precursor.
The DOTP added in the above preparation process is dioctyl terephthalate which is a plasticizer for a PVC material. In a process of preparing the synergistic heat stabilizer, the
DOTP is added in advance as a solvent, thereby avoiding unnecessary addition of other solvents; and a plasticizer is not added anymore in follow-up preparation of the PVC material.
The synergistic heat stabilizer of the present invention is used by adding into a PVC base 2 material to improve the thermal stability of the PVC material. Proportions of the components are: 100 mass parts of PVC resin, 1.0-5.0 mass parts of the butyl titanate, 1.0-5.0 mass parts of the cerium metal soap and 0.1-1.0 mass part of the organic tin heat stabilizer.
Preferred proportions are: 100 mass parts of PVC resin, 1.0-5.0 mass parts of the butyl titanate, 1.0-5.0 mass parts of the cerium metal soap and 0.5 mass part of the organic tin heat stabilizer.
The synergistic heat stabilizer of the present invention is used specifically as follows: the synergistic heat stabilizer precursor is mixed with the PVC base material, and the mixture is stirred at a high speed to obtain a premix; then, the premix is subjected to Banbury mixing in a
Banbury mixer, with a melt temperature of 170-175°C, a screw speed of 40 r/min and a
Banbury mixing time of 2-3 min; the Banbury mixing is finished after a torque is increased sharply and then decreased and kept unchanged; and the mixed materials are taken out and subjected to tableting for 40 seconds in a vulcanizing press at 100°C, to obtain a PVC slice with a thickness of 1 mm, for a follow-up performance test.
The synergistic heat stabilizer of the present invention improves the thermal stability of
PVC in the following way: the PVC is used as a base material, the butyl titanate modified cerium metal soap complex is used as an auxiliary stabilizer, and the organic tin is used as a heat stabilizer; and the butyl titanate has a notable synergistic stabilizing effect on the organic tin and the cerium metal soap, and can effectively improve the thermal stability of the PVC.
In the present invention, the butyl titanate is used for surface modification, and a microwave radiation technology is used as a green and quick preparation method to prepare a
PVC composite film of a butyl titanate modified cerium metal soap and organic tin with different addition amounts; and the hydrogen chloride releasing rates of different composite films are measured with a 195°C conductivity method. The butyl titanate triggers an intense synergistic effect with the cerium metal soap and the organic tin, thereby notably improving the thermal stability and realizing nontoxicity and a good environmental compatibility.
The thermal stability of PVC in the present invention is evaluated with a conductivity or a hydrogen chloride releasing rate, and a test apparatus refers to the ENIS0182-3:2000 standard, namely, high-purity nitrogen is introduced into PVC powder, and the mixture is heated to a constant temperature of 195°C, to observe a change of the conductivity or concentration of the hydrogen chloride absorbed and released by deionized water over time. The PVC is rapidly decomposed to release a hydrogen chloride gas at 180-195°C, and a platinum electrode in a conductivity meter quickly senses a change of the conductivity of hydrogen protons and chlorine 10ns in the deionized water over time. A composite stabilizer is added to suppress the 3 decomposition; and an induction period and a stabilizing time are measured through a conductivity curve, to judge whether the effect of the composite heat stabilizer is good or bad.
Compared with the prior art, the present invention has the following beneficial effects: 1. The modifier adopted by the present invention is butyl titanate which is environmentally compatible and easy for degradation; and when the modifier is used to modify a cerium metal soap as a potential photodecomposition accelerant, the photodegradation of polyvinyl chloride in the environment can be promoted at the end of life; 2. The butyl titanate can promote generation of an electrostatic attraction and a chemical bonding force among the tin, the cerium metal soap and the polyvinyl chloride molecules; 3. The butyl titanate has a notable synergistic stabilizing effect on the methyl tin mercaptide and the cerium metal soap, and can reduce usage of the methyl tin mercaptide, thereby realizing a better effect than a methyl tin mercaptide stabilizer alone and effectively improving the heat resistance of PVC; and 4. The butyl titanate, the methyl tin mercaptide and the cerium metal soap all belong to nontoxic or low-toxicity environment-friendly materials, and completely meet the development requirements for environmental protection home and abroad, thereby having a broad application prospect.
FIG. 1 is a conductivity-time curve of releasing hydrogen chloride by different PVC films in Embodiments 1 and 2. In the figure, the horizontal axis represents heating time/min; the vertical axis represents conductivity/uScm’} the dotted line represents conventional heating; the solid line represents microwave heating; and the composition includes 0.5 part of methyl tin mercaptide, 1 part of butyl titanate, 5 parts of cerium stearate, 50 parts of DOTP and 100 parts of PVC.
Butyl titanate was used as a coupling agent in the present invention, and 1-5 parts of the butyl titanate was added into every 100 parts of PVC.
Cerium stearate was used as an auxiliary stabilizer, and 1-10 parts, preferably 5 parts of the cerium stearate was added into every 100 parts of PVC. (I) Cerium stearate + microwave heating 100 parts of PVC resin S-65, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl 4 tin mercaptide and 5 parts of cerium stearate were fetched. (IT) Cerium stearate + conventional heating 100 parts of PVC resin S-65, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of cerium stearate were fetched.
Control sample + conventional heating 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of lanthanum stearate; 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of calcium stearate; 100 parts of
PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of magnesium stearate; 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of zinc stearate; and 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of calcium- zinc.
Control sample + microwave heating 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of lanthanum stearate; 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of calcium stearate; 100 parts of
PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of magnesium stearate; 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of zinc stearate; and 100 parts of PVC resin, 50 parts of DOTP, 1 part of butyl titanate, 0.5 part of methyl tin mercaptide and 5 parts of calcium- zinc.
Embodiment 1: Preparation of a PVC/butyl titanate-cerium metal soap-organic tin composite film 50 mass parts of DOTP, 1 mass part of butyl titanate, 5 mass parts of a cerium metal soap and 0.5 mass part of an organic tin stabilizer were mixed and dissolved using a microwave radiation technology; a mixed microwave (17% of power output) radiation was started for 15 min in a microwave oven, to obtain a uniform precursor; the obtained precursor was added into 100 mass parts of PVC, and the mixture was stirred at a high speed to obtain a premix; the premix was subjected to Banbury mixing in a small Banbury mixer, with a melt temperature of 170-175°C, a screw speed of 40 r/min and a Banbury mixing time of 2-3 min; the Banbury mixing was finished after a torque was increased sharply and then decreased and kept unchanged; and the mixed materials were taken out and subjected to tableting for 40 seconds in a vulcanizing press at 100°C, to obtain a PVC slice with a thickness of 1 mm.
Embodiment 2: Preparation of a PVC/butyl titanate-cerium metal soap-organic tin composite film mass parts of DOTP, 1 mass part of butyl titanate, 5 mass parts of a cerium metal soap and 0.5 mass part of an organic tin stabilizer were mixed and dissolved using an ultrasonic radiation technology; ultrasonic shaking was started for 1 hour, to obtain a uniform precursor; the obtained precursor was added into 100 mass parts of PVC, and the mixture was stirred at a high speed to obtain a premix; the premix was subjected to Banbury mixing in a small Banbury mixer, with a melt temperature of 170-175°C, a screw speed of 40 r/min and a Banbury mixing time of 2-3 min; the Banbury mixing was finished after a torque was increased sharply and then decreased and kept unchanged; and the mixed materials were taken out and subjected to tableting for 40 seconds in a vulcanizing press at 100°C, to obtain a PVC slice with a thickness of I mm.
Table 1 Conductivity of releasing hydrogen chloride by different PVC films under microwave radiation
Serial No. Component Feed ratio (parts) rn 7 ie h So
Embodiment 1 A/B/C 0.5/5.0/1.0 70 93
Cope A/B/C 0.5/5.0/1.0 75 137
Cp © A/B/C 0.5/5.0/1.0 42 56 es A/B4/C 0.5/5.0/1.0 45 51
Cy A/B/C 0.5/5.0/1.0 53 73
Copa® A/B/C 0.5/5.0/1.0 33 45 (Note: A-methyl tin mercaptide; Bi-cerium stearate; Bz-calcium stearate; B3-magnesium stearate; B4-zinc stearate; Bs-lanthanum stearate; Be-(calcium-zinc)*commercially available goods; C-butyl titanate; all samples contained 100 parts of PVC and 50 parts of DOTP; the power of the microwave oven was 700 W; and the heating intensity was 17% of power output.)
Comparative examples 1-5 adopted a microwave radiation technology:
Comparative example 1: Preparation of a PVC/butyl titanate-calcium metal soap-organic tin composite film 50 mass parts of DOTP, 1 mass part of butyl titanate, 5 mass parts of a calcium metal soap 6 and 0.5 mass part of an organic tin stabilizer were mixed and dissolved using a microwave radiation technology; a mixed microwave (17% of power output) radiation was started for 15 min in a microwave oven, to obtain a uniform precursor; the obtained precursor was added into 100 mass parts of PVC, and the mixture was stirred at a high speed to obtain a premix; the premix was subjected to Banbury mixing in a small Banbury mixer, with a melt temperature of 170-175°C, a screw speed of 40 r/min and a Banbury mixing time of 2-3 min; the Banbury mixing was finished after a torque was increased sharply and then decreased and kept unchanged; and the mixed materials were taken out and subjected to tableting for 40 seconds in a vulcanizing press at 100°C, to obtain a PVC slice with a thickness of 1 mm.
Comparative example 2: Preparation of a PVC/butyl titanate-magnesium metal soap- organic tin composite film mass parts of DOTP, 1 mass part of butyl titanate, 5 mass parts of a magnesium metal soap and 0.5 mass part of an organic tin stabilizer were mixed and dissolved using a microwave radiation technology; a mixed microwave (17% of power output) radiation was started for 15 min in a microwave oven, to obtain a uniform precursor; the obtained precursor was added into 100 mass parts of PVC, and the mixture was stirred at a high speed to obtain a premix; the premix was subjected to Banbury mixing in a small Banbury mixer, with a melt temperature of 170-175°C, a screw speed of 40 r/min and a Banbury mixing time of 2-3 min; the Banbury mixing was finished after a torque was increased sharply and then decreased and kept unchanged; and the mixed materials were taken out and subjected to tableting for 40 seconds in a vulcanizing press at 100°C, to obtain a PVC slice with a thickness of 1 mm.
Comparative example 3: Preparation of a PVC/butyl titanate-zinc metal soap-organic tin composite film 50 mass parts of DOTP, 1 mass part of butyl titanate, 5 mass parts of a zinc metal soap and 0.5 mass part of an organic tin stabilizer were mixed and dissolved using a microwave radiation technology; a mixed microwave (17% of power output) radiation was started for 15 min in a microwave oven, to obtain a uniform precursor; the obtained precursor was added into 100 mass parts of PVC, and the mixture was stirred at a high speed to obtain a premix; the premix was subjected to Banbury mixing in a small Banbury mixer, with a melt temperature of 170- 175°C, a screw speed of 40 r/min and a Banbury mixing time of 2-3 min; the Banbury mixing was finished after a torque was increased sharply and then decreased and kept unchanged; and the mixed materials were taken out and subjected to tableting for 40 seconds in a vulcanizing press at 100°C, to obtain a PVC slice with a thickness of I mm.
Comparative example 4: Preparation of a PVC/butyl titanate-lanthanum metal soap- 7 organic tin composite film mass parts of DOTP, 1 mass part of butyl titanate, 5 mass parts of a lanthanum metal soap and 0.5 mass part of an organic tin stabilizer were mixed and dissolved using a microwave radiation technology; a mixed microwave (17% of power output) radiation was started for 15 min in a microwave oven, to obtain a uniform precursor; the obtained precursor was added into 100 mass parts of PVC, and the mixture was stirred at a high speed to obtain a premix; the premix was subjected to Banbury mixing in a small Banbury mixer, with a melt temperature of 170-175°C, a screw speed of 40 r/min and a Banbury mixing time of 2-3 min; the Banbury mixing was finished after a torque was increased sharply and then decreased and kept unchanged; and the mixed materials were taken out and subjected to tableting for 40 seconds in a vulcanizing press at 100°C, to obtain a PVC slice with a thickness of 1 mm.
Comparative example 5: Preparation of a PVC/butyl titanate-(calcium-zinc)*-organic tin composite film 50 mass parts of DOTP, 1 mass part of butyl titanate, 5 mass parts of (calcium-zinc)* and 0.5 mass part of an organic tin stabilizer were mixed and dissolved using a microwave radiation technology; a mixed microwave (17% of power output) radiation was started for 15 min in a microwave oven, to obtain a uniform precursor; the obtained precursor was added into 100 mass parts of PVC, and the mixture was stirred at a high speed to obtain a premix; the premix was subjected to Banbury mixing in a small Banbury mixer, with a melt temperature of 170- 175°C, a screw speed of 40 r/min and a Banbury mixing time of 2-3 min; the Banbury mixing was finished after a torque was increased sharply and then decreased and kept unchanged; and the mixed materials were taken out and subjected to tableting for 40 seconds in a vulcanizing press at 100°C, to obtain a PVC slice with a thickness of 1 mm.
Comparative examples 6-10 adopted ultrasonic radiation:
Comparative example 6: Preparation of a PVC/butyl titanate-calcium metal soap-organic tin composite film 100 mass parts of PVC, 50 mass parts of DOTP, 1 mass part of butyl titanate, 5 mass parts of a calcium metal soap and 0.5 mass part of an organic tin stabilizer were mixed and dissolved using an ultrasonic radiation technology; ultrasonic stirring was performed for 1 hour at 40°C, to obtain a uniform premix; the obtained premix was subjected to Banbury mixing in a small
Banbury mixer, with a melt temperature of 170-175°C, a screw speed of 40 r/min and a
Banbury mixing time of 2-3 min; the Banbury mixing was finished after a torque was increased sharply and then decreased and kept unchanged; and the mixed materials were taken out and subjected to tableting for 40 seconds in a vulcanizing press at 100°C, to obtain a PVC slice 8 with a thickness of 1 mm.
Comparative example 7: Preparation of a PVC/butyl titanate-magnesium metal soap- organic tin composite film 100 mass parts of PVC, 50 mass parts of DOTP, 1 mass part of butyl titanate, 5 mass parts of a magnesium metal soap and 0.5 mass part of an organic tin stabilizer were mixed and dissolved using an ultrasonic radiation technology; ultrasonic stirring was performed for 1 hour at 40°C, to obtain a uniform premix; the obtained premix was subjected to Banbury mixing in a small Banbury mixer, with a melt temperature of 170-175°C, a screw speed of 40 r/min and a Banbury mixing time of 2-3 min; the Banbury mixing was finished after a torque was increased sharply and then decreased and kept unchanged; and the mixed materials were taken out and subjected to tableting for 40 seconds in a vulcanizing press at 100°C, to obtain a PVC slice with a thickness of 1 mm.
Comparative example 8: Preparation of a PVC/butyl titanate-zinc metal soap-organic tin composite film 100 mass parts of PVC, 50 mass parts of DOTP, 1 mass part of butyl titanate, 5 mass parts of a zinc metal soap and 0.5 mass part of an organic tin stabilizer were mixed and dissolved using an ultrasonic radiation technology; ultrasonic stirring was performed for 1 hour at 40°C, to obtain a uniform premix; the obtained premix was subjected to Banbury mixing in a small
Banbury mixer, with a melt temperature of 170-175°C, a screw speed of 40 r/min and a
Banbury mixing time of 2-3 min; the Banbury mixing was finished after a torque was increased sharply and then decreased and kept unchanged; and the mixed materials were taken out and subjected to tableting for 40 seconds in a vulcanizing press at 100°C, to obtain a PVC slice with a thickness of 1 mm.
Comparative example 9: Preparation of a PVC/butyl titanate-lanthanum metal soap- organic tin composite film 100 mass parts of PVC, 50 mass parts of DOTP, 1 mass part of butyl titanate, 5 mass parts of a lanthanum metal soap and 0.5 mass part of an organic tin stabilizer were mixed and dissolved using an ultrasonic radiation technology; ultrasonic stirring was performed for 1 hour at 40°C, to obtain a uniform premix; the obtained premix was subjected to Banbury mixing in a small Banbury mixer, with a melt temperature of 170-175°C, a screw speed of 40 r/min and a Banbury mixing time of 2-3 min; the Banbury mixing was finished after a torque was increased sharply and then decreased and kept unchanged; and the mixed materials were taken out and subjected to tableting for 40 seconds in a vulcanizing press at 100°C, to obtain a PVC slice with a thickness of 1 mm. 9
Comparative example 10: Preparation of a PVC/butyl titanate-(calcium-zine)*-organic tin composite film 100 mass parts of PVC, 50 mass parts of DOTP, 1 mass part of butyl titanate, 5 mass parts of (calcium-zinc)* and 0.5 mass part of an organic tin stabilizer were mixed and dissolved using an ultrasonic radiation technology; ultrasonic stirring was performed for 1 hour at 40°C, to obtain a uniform premix; the obtained premix was subjected to Banbury mixing in a small
Banbury mixer, with a melt temperature of 170-175°C, a screw speed of 40 r/min and a
Banbury mixing time of 2-3 min; the Banbury mixing was finished after a torque was increased sharply and then decreased and kept unchanged; and the mixed materials were taken out and subjected to tableting for 40 seconds in a vulcanizing press at 100°C, to obtain a PVC slice with a thickness of 1 mm.
Table 2 Conductivity of releasing hydrogen chloride by different PVC films under conventional heating
Serial No. Component Feed ratio (parts) rom T io jr
Embodiment 2 A/B/C 0.5/5.0/1.0 60 87 eG: A/B2/C 0.5/5.0/1.0 88 126
Coe A/B/C 0.5/5.0/1.0 45 65 es A/B4/C 0.5/5.0/1.0 57 60 eon A/B5/C 0.5/5.0/1.0 60 82
PS A/Bs/C 0.5/5.0/1.0 36 47 (Note: A-methyl tin mercaptide; Bi-cerium stearate; B2-calcium stearate; B3-magnesium stearate; Ba-zinc stearate; Bs-lanthanum stearate; Bs-(calcium-zinc}* commercially available goods; C-butyl titanate; all samples contained 100 parts of PVC and 50 parts of DOTP.)
A method of evaluating the thermal stability of PVC includes: the conductivity of a hydrogen chloride releasing aqueous solution was measured by referring to the ENIS0182- 3:2000 standard; high-purity nitrogen was introduced into a PVC powder heating test tube; oil bathing was performed using silicone oil while the heating temperature was 195°C; and a curve of the conductivity of hydrogen chloride absorbed and released by deionized water changing over time was observed.
A PVC sample was decomposed to release a hydrogen chloride gas at 180-195°C, and a platinum electrode in a conductivity meter quickly sensed a change of the conductivity of hydrogen protons and chlorine ions in the deionized water. A composite stabilizer was added to suppress the decomposition; and an induction period and a stabilizing time were measured through the conductivity curve, to judge whether the effect of the heat stabilizer is good or bad.
It can be seen from Table 1, Table 2 and FIG. 1 that, in the conventional heating of a plasticized PVC film consisting of calcium, magnesium, zinc, lanthanum and cerium metal soaps, (calcium-zinc)*, organic tin and a butyl titanate coupling agent, the induction periods for releasing hydrogen chloride through PVC thermal degradation are 60 min, 88 min, 45 min, 57 min, 60 min and 36 min respectively in a nitrogen atmosphere at 195°C, while in the same conditions, through 15 min of microwave (17% of power output) radiation, corresponding induction periods for releasing hydrogen chloride through PVC thermal degradation are 70 min, 75 min, 42 min, 45 min, 53 min and 33 min respectively, indicating that the induction period for PVC thermal degradation of the cerium-containing metal soap alone is increased by min, and the induction periods of the calcium, magnesium, zinc and lanthanum metal soaps and the (calcium-zinc)* are reduced by 13 min, 3 min, 12 min, 7 min and 3 min respectively.
Therefore, except the cerium metal soaps of Embodiment 1 and Embodiment 2, as for the microwave heating versus the conventional heating, only the cerium metal soap can enhance the thermal stability of the PVC film. For the calcium, magnesium, zinc, lanthanum metal soaps and the (calcium-zinc)*, the heat resistance stability of the PVC film is reduced as for the microwave heating versus the conventional heating, namely, the stability has a declining trend, as shown in Comparative examples 1-10.
Table 3 Conductivity of releasing hydrogen chloride by PVC film with different radiation time
Microwave T induction 1 stable
Serial No. Component Feed ratio (parts) radiation period period/min (100 time/min /min uSem™)
Embodiment 1 A/B/C 0.5/5.0/1.0 15 70 93
Embodiment 3 A/Bi/C 0.5/5.0/1.0 5 50 86 (Note: A-methyl tin mercaptide; Bi-cerium stearate; C-butyl titanate; all samples contained 100 parts of PVC and 50 parts of DOTP; the power of the microwave oven was 700 W; and the heating intensity was 17% of power output.)
Table 3 shows the conductivity of releasing hydrogen chloride by the PVC film with 11 different radiation time. When the microwave radiation time is increased from 5 min in
Embodiment 3 to 15 min in Embodiment 1, the induction period for releasing hydrogen chloride by the PVC film is increased from 50 min to 70 min, indicating that heat resistance of the PVC film can be improved by increasing the radiation time. 12
Claims (9)
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