CN105566810B - Polyvinyl-chloride use zinc soap mannitol composite thermal stabilizer, preparation method and application - Google Patents
Polyvinyl-chloride use zinc soap mannitol composite thermal stabilizer, preparation method and application Download PDFInfo
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- CN105566810B CN105566810B CN201610080299.5A CN201610080299A CN105566810B CN 105566810 B CN105566810 B CN 105566810B CN 201610080299 A CN201610080299 A CN 201610080299A CN 105566810 B CN105566810 B CN 105566810B
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- Prior art keywords
- zinc
- mannitol
- soap
- zinc soap
- stabilizer
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- 239000011701 zinc Substances 0.000 title claims abstract description 80
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 80
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000000594 mannitol Substances 0.000 title claims abstract description 70
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 50
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 49
- 229930195725 Mannitol Natural products 0.000 title claims abstract description 45
- 235000010355 mannitol Nutrition 0.000 title claims abstract description 45
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 title claims abstract description 43
- 239000000344 soap Substances 0.000 title claims abstract description 39
- 239000003017 thermal stabilizer Substances 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000012760 heat stabilizer Substances 0.000 claims abstract description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- JNYAEWCLZODPBN-KVTDHHQDSA-N (2r,3r,4r)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical compound OC[C@@H](O)[C@H]1OC[C@@H](O)[C@H]1O JNYAEWCLZODPBN-KVTDHHQDSA-N 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 15
- -1 alcohol compound Chemical class 0.000 claims description 12
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 229940098697 zinc laurate Drugs 0.000 claims description 4
- GPYYEEJOMCKTPR-UHFFFAOYSA-L zinc;dodecanoate Chemical compound [Zn+2].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O GPYYEEJOMCKTPR-UHFFFAOYSA-L 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229940012185 zinc palmitate Drugs 0.000 claims description 3
- LPEBYPDZMWMCLZ-CVBJKYQLSA-L zinc;(z)-octadec-9-enoate Chemical compound [Zn+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O LPEBYPDZMWMCLZ-CVBJKYQLSA-L 0.000 claims description 3
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 3
- GJAPSKMAVXDBIU-UHFFFAOYSA-L zinc;hexadecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O GJAPSKMAVXDBIU-UHFFFAOYSA-L 0.000 claims description 3
- GBFLQPIIIRJQLU-UHFFFAOYSA-L zinc;tetradecanoate Chemical compound [Zn+2].CCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCC([O-])=O GBFLQPIIIRJQLU-UHFFFAOYSA-L 0.000 claims description 3
- 239000006057 Non-nutritive feed additive Substances 0.000 claims description 2
- 235000021355 Stearic acid Nutrition 0.000 claims description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 230000006641 stabilisation Effects 0.000 claims description 2
- 238000011105 stabilization Methods 0.000 claims description 2
- 239000008117 stearic acid Substances 0.000 claims description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 claims 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 claims 2
- 235000020778 linoleic acid Nutrition 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 10
- 238000004040 coloring Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 230000007774 longterm Effects 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 235000009508 confectionery Nutrition 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 21
- 229910000831 Steel Inorganic materials 0.000 description 9
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 9
- 238000013019 agitation Methods 0.000 description 9
- 239000012299 nitrogen atmosphere Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 5
- 230000007547 defect Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000004500 asepsis Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000007731 hot pressing Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000008301 phosphite esters Chemical class 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000000518 rheometry Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000004605 External Lubricant Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000003490 calendering Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002305 electric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000002649 leather substitute Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- ODNJVAVDJKOYFK-GRVYQHKQSA-L zinc;(9z,12z)-octadeca-9,12-dienoate Chemical compound [Zn+2].CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O.CCCCC\C=C/C\C=C/CCCCCCCC([O-])=O ODNJVAVDJKOYFK-GRVYQHKQSA-L 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
- C08K5/09—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
- C08K5/05—Alcohols; Metal alcoholates
- C08K5/053—Polyhydroxylic alcohols
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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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 invention discloses a kind of polyvinyl-chloride use zinc soap mannitol composite thermal stabilizer, preparation method and application, the compound that the heat stabilizer is generated after being reacted for zinc soap with mannitol, including zinc soap, zinc soap sweet dew alcohol complex, mannitol, anhydromannitol.Extensively, technique is simple and environmentally-friendly, and cost is low for raw material sources of the present invention, and production efficiency is high, and properties of product are easy to regulation and control.This composite thermal stabilizer initial coloring is good, good with PVC matrix compatibility, easily scattered, it can effectively improve PVC long-term thermal stability, have good inside and outside lubricity concurrently, high comprehensive performance solves the not good problem of current environment-friendly type PVC heat stabilizer thermostable effect.
Description
Technical field
The present invention relates to high polymer material auxiliary agent field, and in particular to a kind of polyvinyl-chloride use zinc soap-mannitol compound thermal
Stabilizer, preparation method and application.
Background technology
Polyvinyl chloride (PVC) is one of earliest industrialized plastics variety, and current production rate occupies second, with excellent
The features such as mechanical performance, good electrical property, resistance to chemical corrosion, anti-flammability, hypotonicity of gas and steam.PVC is with it
Excellent combination property, diversified kind, cheap price, are widely used in building, chemical industry, electric and packaging material
Etc. industry.PVC processing characteristicies are good, can be processed by modes such as extrusion, blowing, injection, calendering, coatings, mainly for the production of
The soft goods such as the boardy products such as tubing, sheet material, profile shapes and artificial leather, film, cable, seal.
PVC glass transition temperature is 82 DEG C, is typically processed in the range of 160~180 DEG C.Because PVC exists
Some active defect chlorine atoms can be produced in building-up process, degraded is begun to when temperature is more than 140 DEG C, PVC trees are had a strong impact on
The performance of fat, therefore, it is necessary to add the heat stabilizer of function admirable in PVC process.In general, heat stabilizer can
To improve PVC heat endurance by following approach：(1) defect chlorine atom active in displacement PVC chains, restrains PVC product
Initial coloration；(2) hydrogen chloride discharged in PVC degradation processes is caught, suppresses its self-catalysis degradation；(3) can be with conjugation
Addition reaction occurs for alkene structures, shortens the length of conjugated alkene, reduces the discoloration of product.
Current commercialized heat stabilizer is wide in variety, and conventional mainly has lead salt type thermal stabilizing agent, organic tin heat steady
Determine agent, metal soap thermal stabilizerses three major types.Lead salt type thermal stabilizing agent is cheap, thermostable effect is good, but lead salt toxicity is big,
It is big to environment and biohazard, the requirement of current environmental protection is not met, is gradually replaced by the heat stabilizer of other kinds.
Organic tin heat stabilizer has versatility, security and efficient heat endurance, but price is high, limits to a certain extent
Popularization and application of the organo-tin het stabilizer in China.And metal soap thermal stabilizerses, it is the most frequently used for calcium zinc heat stabilizer, it is nontoxic
Environmental protection, cheap, lubricity is good, but thermostable effect is not good, it is difficult to meet some occasions, the production of such as boardy product will
Ask.
Calcium zinc heat stabilizer is typical metal soap thermal stabilizerses, and zinc soap can replace defect chlorine atom and absorb chlorination
Hydrogen, but the zinc chloride of generation is a kind of strong Lewis acid, easily causes zinc to burn, it is necessary to be used cooperatively with calcium soap, restrains zinc
Burn, but individually calcium zinc heat stabilizer effect is not good.In order to improve the thermostable effect of calcium zinc heat stabilizer, such as patent document
CN 102417677A, CN 103435944A and CN 103865196A etc. report that calcium zinc heat stabilizer and auxiliary heat stabilizer are such as
Phosphite ester, beta-diketon, epoxide etc. are compounded, and have synergy between each component, can improve initial coloring and long-term
Heat endurance, high comprehensive performance.But phosphite ester discharges niff in process, beta-diketon easily causes
Filled PVC product is general red.Polyalcohol can be produced as auxiliary heat stabilizer and good cooperate with work with other thermal stabilizer components
With, have document report, by pentaerythrite be applied to calcium zinc heat stabilizer system, PVC lubricity can be improved, and improve its length
Phase heat endurance.(Ming Wang,Jiayou Xu,Hong Wu,Shaoyun Guo,Effect of pentaerythritol
and organic tin with calcium/zinc stearates on the stabilization of poly
(vinyl chloride),Polym.Degrad.Stab.,2006,91,2101-2109).But pentaerythrite fusing point is high, with
PVC poor compatibilities, are easily separated out.
The content of the invention
The present invention is prepared for a kind of asepsis environment-protecting, initial coloring is good, lubricity is excellent, the PVC that is easily dispersed zinc soap-sweet
Reveal alcohol composite thermal stabilizer.
Invention also provides a kind of preparation method of zinc soap-mannitol composite thermal stabilizer, this method technique is simple,
Easy to operate, with short production cycle, raw material sources are extensive, it is adaptable to industrialized production.
Present invention also offers a kind of polrvinyl chloride product, the product uses above-mentioned zinc soap-mannitol composite thermal stabilizer,
Stability is high.
A kind of zinc soap-mannitol composite thermal stabilizer, the compound generated after zinc soap and mannitol reaction, including zinc
Soap, zinc soap-sweet dew alcohol complex, mannitol, anhydromannitol.
A kind of zinc soap-mannitol composite thermal stabilizer, the wherein mol ratio of zinc soap and mannitol are 0.1~10.Work as zinc soap
When content is relatively low, the ability of the defect chlorine atom in displacement PVC is poor, and initial coloring is not good, and interior lubricity is not good, high
Friction is big in molecule interchain, easily causes degraded；When mannitol content is low, the synergy of zinc soap and mannitol is not enough, holds
Zinc burning is also easy to produce, long-term thermal stability is not enough, and outer lubricity is poor, and counter balance torque is larger during processing.Preferably, described
Zinc soap and the mol ratio of mannitol be 0.5~3, zinc soap and mannitol synergy are obvious within this range, initial coloring
Good with long-term thermal stability, inside and outside lubricity is balanced, and resultant effect is excellent.
Zinc soap of the present invention is zinc Isoocatanoate, zinc laurate, Zinc tetradecanoate, zinc palmitate, zinc stearate, oleic acid
One or more in zinc, zinc linoleate, zinc ricinate.It is preferred to use zinc stearate.
Reaction condition prepared by zinc soap of the present invention-mannitol compound is as follows：In atmosphere of inert gases, by zinc soap
140~220 DEG C are heated to mannitol, stirring is lower to react 0.5~8 hour, and it is thermally-stabilised that cooling obtains zinc soap-mannitol compound
Agent.
Preferably, described reaction temperature is 180~200 DEG C, and when reaction temperature is low, zinc soap and mannitol reaction speed
Slowly；When temperature is too high, oxidation reaction can occur for zinc soap and mannitol.
Preferably, the described reaction time is 2~4 hours, the reaction time is too short, and zinc soap and mannitol reaction are not filled
Point；Reaction time is oversize, and the extent of reaction is without being obviously improved, and zinc soap and mannitol oxidation are than more serious.
Preferably, described stir speed (S.S.) is 100~250rpm, the mannitol and zinc soap of liquid are incompatible, stirring speed
Rate is too low, mixes and reacts insufficient；Stir speed (S.S.) is too high, and mixed effect wastes electric energy without being obviously improved；As further excellent
Choosing, described stir speed (S.S.) is 100~200rpm.
Preferably, described inert gas is the one or more in nitrogen and argon gas, it is preferred to use nitrogen.
The characteristics of zinc soap-mannitol compound in the present invention is using zinc soap and mannitol as reactant, in high temperature bar
Zinc soap-sweet dew alcohol complex, and the Isosorbide-5-Nitrae-anhydromannitol and Isosorbide-5-Nitrae that mannitol intramolecular dehydration is formed are generated under part:3,6-
Two anhydromannitols, final product is zinc soap-sweet dew alcohol complex, zinc soap, mannitol, the mixture of anhydromannitol.
Present invention also offers a kind of polrvinyl chloride product, including stabilizer, the stabilizer is in above-mentioned technical proposal
The preparation method of polyvinyl-chloride use zinc soap-mannitol composite thermal stabilizer described in any technical scheme is prepared.
Preferably, the weight percent content of the stabilizer is 2~6%.
Preferably, the polrvinyl chloride product includes：
Zinc soap-sweet dew alcohol complex and zinc soap can react with the defect chlorine atom in PVC in the present invention, suppress PVC and add
The coloring at work initial stage, the polarity of zinc soap-sweet dew alcohol complex and zinc soap is close with PVC in addition, can be reduced as in-lubricant
The friction of PVC molecules interchain in process, reduces and is degraded caused by friction produces hot-spot.Zinc soap-mannitol complexing
Thing and zinc soap energy absorbing hydrogen chloride, eliminate self-catalysis degradation reaction, but produce the sour zinc chloride of very strong Lewis, easily cause zinc
Burn.Mannitol and anhydromannitol component in zinc soap-mannitol compound contain great amount of hydroxy group, can be coordinated with zinc chloride,
The Lewis for reducing zinc chloride is acid, so as to suppress zinc burning, improves PVC long-term thermal stability.Mannitol and anhydromannitol pole
Property it is larger, work in-process can play a part of external lubricant, reduce PVC and intermetallic friction.Described zinc soap-mannitol
Compound can be used as PVC heat stabilizer, synergy be produced between the compound each component, not only with preferable initial coloration
Property, and long-term thermal stability is good, has inside and outside lubricity concurrently, high comprehensive performance.
The mannitol fusing point that the present invention is selected is 166 DEG C, less than the processing temperature of PVC boardy products, be can ensure that processed
It is well dispersed in journey, and mannitol is from biological purification and glucose reduction, is renewable resource.It is thermally-stabilised with other auxiliary
Agent is compared, and either production process or material meet the requirement of asepsis environment-protecting in itself,.By the way that zinc soap is answered with mannitol
Close, zinc burning can be restrained, the environmentally friendly heat stabilizer that a kind of initial coloring is good, lubricity is excellent, be easily dispersed, mesh is obtained
Before there is no zinc soap-mannitol composite thermal stabilizer and the report of preparation method.
Zinc soap prepared by the present invention-mannitol compound heat stabilizer, asepsis environment-protecting, initial coloring is good, and fusing point is low, easily
It is scattered, it is good with PVC matrix compatibility, have good inside and outside lubricity concurrently, solve current environment-friendly type PVC heat stabilizer thermally-stabilised
The not good problem of effect.Zinc soap-mannitol compound heat stabilizer of the present invention, preparation method is simple, and raw material sources extensively, can
Industrialized production, substitutes calcium zinc stabilizer common in the market, with good Commercial Prospect.
Brief description of the drawings
Fig. 1 is the infrared light of zinc stearate (a), mannitol (c) and zinc stearate-mannitol compound (b) in embodiment 1
Spectrum.
Embodiment
Embodiment 1
By zinc stearate (18.96g, 0.03mol) and mannitol (5.47g, 0.03mol) according to mol ratio 1:1 ratio
It is added in 500mL three-necked flasks, using mechanical agitation, under stir speed (S.S.) is 100rpm, nitrogen atmosphere, in 200 DEG C of oil baths
Reaction 2 hours.After cooling, product is ground to form into fine powder, is sieved and sieved with 200 mesh steel, obtain zinc stearate-mannitol compound.
Characterize zinc stearate, mannitol and zinc stearate-mannitol respectively using Fourier infrared spectrograph and be combined materialization
Structure is learned, as a result as shown in Figure 1.Pressed disc method sample preparation, 4000~400cm of scanning range are ground using KBr-1。
In Fig. 1, a is the infrared spectrum of zinc stearate, and b is the infrared spectrum of zinc stearate-mannitol compound, and c is sweet
Reveal the infrared spectrum of alcohol.As shown in a in Fig. 1,2848cm-1And 2918cm-1For the stretching vibration absworption peak of C-H in stearate radical,
1398cm-1And 1464cm-1For the flexural vibrations absworption peak of C-H in stearate radical, 1540cm-1Flexible for carboxylic acid ion shakes
Dynamic absworption peak.As shown in c in Fig. 1,3399cm-1And 3287cm-1Respectively the stretching vibration of mannitol primary hydroxyl and secondary hydroxyl is inhaled
Receive peak, 2900cm-1To 2980cm-1For mannitol C-H stretching vibration absworption peak, 1422cm-1And 1282cm-1For mannitol C-H
Flexural vibrations absworption peak, 1082cm-1And 1020cm-1It is the flexural vibrations absworption peak of hydroxyl.As shown in b in Fig. 1, by anti-
Hydroxyl absorption peak has significant change after answering, and three new absworption peak (1194cm occurs in fingerprint region-1、1262cm-1With
1325cm-1), illustrate that C-H chemical environment changes, mannitol reacts；In addition in 725cm-1There is new suction in place
Receive, the hydroxyl and zinc ion for illustrating mannitol have coordination.
Embodiment 2
By zinc stearate (18.96g, 0.03mol) and mannitol (1.82g, 0.01mol) according to mol ratio 3:1 ratio
It is added in 500mL three-necked flasks, it is anti-in 180 DEG C of oil baths under stir speed (S.S.) is 50rpm, nitrogen atmosphere using mechanical agitation
Answer 4 hours.After cooling, product is ground to form into fine powder, is sieved and sieved with 200 mesh steel, obtain zinc stearate-mannitol compound.
Embodiment 3
By zinc laurate (13.92g, 0.03mol) and mannitol (0.55g, 0.003mol) according to mol ratio 10:1 ratio
Example is added in 500mL three-necked flasks, using mechanical agitation, under stir speed (S.S.) is 250rpm, nitrogen atmosphere, in 140 DEG C of oil baths
Middle reaction 8 hours.After cooling, product is ground to form into fine powder, is sieved and sieved with 200 mesh steel, zinc laurate-mannitol is obtained and is combined
Thing.
Embodiment 4
By zinc ricinate (9.90g, 0.015mol) and mannitol (5.47g, 0.03mol) according to mol ratio 0.5:1
Ratio is added in 500mL three-necked flasks, using mechanical agitation, under stir speed (S.S.) is 150rpm, nitrogen atmosphere, in 190 DEG C of oil
Reacted 3 hours in bath.After cooling, product is ground to form into fine powder, is sieved and sieved with 200 mesh steel, obtain zinc ricinate-mannitol multiple
Compound.
Embodiment 5
By zinc stearate (9.90g, 0.015mol) and mannitol (13.66g, 0.075mol) according to mol ratio 0.2:1
Ratio is added in 500mL three-necked flasks, using mechanical agitation, under stir speed (S.S.) is 200rpm, nitrogen atmosphere, in 210 DEG C of oil
Reacted 1 hour in bath.After cooling, product is ground to form into fine powder, is sieved and sieved with 200 mesh steel, zinc stearate-mannitol is obtained and is combined
Thing.
Embodiment 6
By zinc stearate (17.70g, 0.028mol) and mannitol (0.73g, 0.004mol) according to mol ratio 7:1 ratio
Example is added in 500mL three-necked flasks, using mechanical agitation, under stir speed (S.S.) is 50rpm, nitrogen atmosphere, in 220 DEG C of oil baths
Reaction 0.5 hour.After cooling, product is ground to form into fine powder, is sieved and sieved with 200 mesh steel, zinc stearate-mannitol is obtained and is combined
Thing.
Embodiment 7
By zinc oleate (6.28g, 0.01mol) and mannitol (18.17g, 0.1mol) according to mol ratio 0.1:1 ratio adds
Enter into 500mL three-necked flasks, using mechanical agitation, under stir speed (S.S.) is 50rpm, nitrogen atmosphere, reacted in 160 DEG C of oil baths
5 hours.After cooling, product is ground to form into fine powder, is sieved and sieved with 200 mesh steel, obtain zinc oleate-mannitol compound.
Comparative example 1
Zinc stearate (18.96g, 0.03mol) is added in 500mL three-necked flasks, using mechanical agitation, stir speed (S.S.)
For 100rpm, under nitrogen atmosphere, reacted 2 hours in 200 DEG C of oil baths.After cooling, product is ground to form into fine powder, with 200 mesh steel
Sieve screening.
Comparative example 2
Mannitol (18.22g, 0.1mol) is added in 500mL three-necked flasks, using mechanical agitation, stir speed (S.S.) is
Under 100rpm, nitrogen atmosphere, reacted 2 hours in 200 DEG C of oil baths.After cooling, product is ground to form into fine powder, sieved with 200 mesh steel
Screening.
PVC sample is prepared and rheology testing
According to mass ratio by 4 parts of heat stabilizers, 100 parts of polyvinyl chloride (Xingjiang Tianye Co., SG-5), 3 parts of ACR processing aids
(Shandong Ruifeng Polymer Material Co., Ltd. produces, LS-01), 7 parts of haloflex (Zibo Huaxing Additives Co., Ltd.
Production, 135A), 0.5 part of stearic acid, 0.5 part of paraffin is through high-speed mixer mixing 10min.65g Premixed samples are taken to exist
Banburying and rheology testing are carried out in Brabender torque rheometers, temperature is 180 DEG C, and rotating speed is 40rotor/min, is mixed
The refining time is 10min, records rheological curve.After banburying terminates, well mixed PVC sample is taken out while hot, in compression molding
180 DEG C of hot pressing 5min, are made sheet in machine.
Influence of the heat stabilizer of table 1 to processing characteristics
Note：Certain commercially available brand calcium zinc heat stabilizer (model MC 123R)
Shown by the result of table 1, zinc soap-mannitol compound of the invention can improve PVC processing characteristics, promote modeling
Change, reduce fusion time, and reduce counter balance torque, play the effect of interior lubrication.
Congo red method determines PVC heat-stable time
According to standard GB/T/T 2917.1-2002《Blend and product based on vinyl chloride homo and copolymer exist
Hydrogen chloride and the measure congo red method of any other acid product are released during high temperature》, mixed PVC prints are shredded, weighed
1.0g samples, are added in test tube, determine Congo red heat-stable time.Test temperature is 180 DEG C, Congored test paper lower end distance
Sample 2cm.
The Congo red heat-stable time of table 2
Shown by the result of table 2, the heat that zinc soap-mannitol compound that the present invention is prepared can obviously improve PVC is steady
It is qualitative；The compound that particularly embodiment 1, embodiment 2, embodiment 4 and embodiment 5 are prepared, heat-stable time exists
More than 49min, significantly larger than calcium zinc heat stabilizer heat-stable time.
Heat ageing baking oven is tested and PVC measuring brightnesses
PVC after hot pressing is cut into 2cm × 2cm print, is placed on aluminium sheet.The air blast that aluminium sheet is put into 180 DEG C is dried
Thermal ageing test is carried out in case, sample is taken out until the complete blackening of batten every 10min.According to standard GB/T 2913-82
《Plastics whiteness test method》, the whiteness of PVC prints is measured using Blue Whiteness analyzer.
Whiteness experimental result (the unit of table 3：%)
Shown by the result of table 3, zinc soap-mannitol compound of the invention can obviously improve PVC initial coloring and
Long-term thermal stability.
Claims (6)
1. a kind of polyvinyl-chloride use zinc soap-mannitol composite thermal stabilizer, it is characterised in that after zinc soap and mannitol reaction
Arrive, mainly including zinc soap-sweet dew alcohol complex, zinc soap, mannitol, anhydromannitol；
Described zinc soap is zinc Isoocatanoate, zinc laurate, Zinc tetradecanoate, zinc palmitate, zinc stearate, zinc oleate, linoleic acid
One or more in zinc, zinc ricinate；Described zinc soap and the mol ratio of mannitol are（0.1~10）：1.
2. a kind of preparation method of polyvinyl-chloride use zinc soap-mannitol composite thermal stabilizer, it is characterised in that including：In inertia
In atmosphere, zinc soap and mannitol are heated to 140 ~ 220 °C, the lower reaction of stirring 0.5 ~ 8 hour, cooling obtains zinc soap-sweet
Reveal alcohol compound heat stabilizer；
Described zinc soap is zinc Isoocatanoate, zinc laurate, Zinc tetradecanoate, zinc palmitate, zinc stearate, zinc oleate, linoleic acid
One or more in zinc, zinc ricinate；Described zinc soap and the mol ratio of mannitol are（0.1~10）：1.
3. the preparation method of polyvinyl-chloride use zinc soap-mannitol composite thermal stabilizer according to claim 2, its feature exists
In described inert gas is the one or more in nitrogen, argon gas.
4. a kind of polrvinyl chloride product, including stabilizer, it is characterised in that the stabilizer is poly- described in Claims 2 or 3
Vinyl chloride is prepared with the preparation method of zinc soap-mannitol composite thermal stabilizer.
5. polrvinyl chloride product according to claim 4, it is characterised in that in the polrvinyl chloride product, the stabilization
The weight percent content of agent is 2 ~ 6%.
6. polrvinyl chloride product according to claim 4, it is characterised in that including：
2 ~ 6 parts of heat stabilizer
100 parts of polyvinyl chloride
1 ~ 4 part of ACR processing aids
5 ~ 10 parts of haloflex
0.1 ~ 1 part of stearic acid
0.1 ~ 1 part of paraffin.
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