CN100497467C - Epoxy-zinc soap compound as heat stabilizer for polyvinyl chloride plastic formula - Google Patents
Epoxy-zinc soap compound as heat stabilizer for polyvinyl chloride plastic formula Download PDFInfo
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- CN100497467C CN100497467C CNB2005100369695A CN200510036969A CN100497467C CN 100497467 C CN100497467 C CN 100497467C CN B2005100369695 A CNB2005100369695 A CN B2005100369695A CN 200510036969 A CN200510036969 A CN 200510036969A CN 100497467 C CN100497467 C CN 100497467C
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Abstract
The present invention discloses one kind of epoxy-zinc soap compound as heat stabilizer for compounding polyvinyl chloride plastic. The heat stabilizer includes epoxy-zinc soap compound as main stabilizer, organic compound as co-stabilizer, and polyethylene as outer lubricant, and may also includes anionic laminated material, antioxidant, inner lubricant and other assistants. The stabilizer system may be used in compounding plasticized and unplasticized polyvinyl chloride plastic. The stabilizer is superior to available calcium-zinc stabilizer as far as the performance of polyvinyl chloride product.
Description
Technical field
The present invention relates to polymeric material field, relate to specifically and a kind ofly be used for that polyvinyl chloride resin is extruded, the compound zinc soap thermo-stabilizer of injection moulding processing purposes.
Background technology
Thermo-stabilizer is used in the calcium zinc class polyvinyl chloride of supply processing in the market, mainly is applicable to the processing of PVC soft goods; When the man-hour that adds that is used for the hard product, stable performance is not enough or make goods produce initial coloration easily.These drawbacks limit they application in the PVC boardy product.
The Chinese patent publication number is CN 1091757A, the patent of invention of right of priority 92.5.27 US 889551 discloses a kind of additive for polymer compositions, is with organo-tin compound or/and organic zinc compound, epoxide, lubricant are that fundamental component combines.The advantage of this invention is, by the ratio of epoxide in the additive system and organic zinc compound is adjusted to optimum value, and adjust the proper equilibrium of stablizer and lubricant necessarily, in PVC melt-processed process, can improve the thermostability of fast fast thawing stream, and do not form black particle, reduce incrustation or accumulation on processing units.But this invention is not suitable for the melt-processed of hard product such as PVC plumbing tubing, section bar because of bigger as one of base stock and content with epoxide with plastification.
Summary of the invention
Purpose of the present invention in order to overcome existing polyvinyl chloride processing with the deficiency that thermo-stabilizer exists in the PVC boardy product is used, provides a kind of epoxy composite zinc soap thermo-stabilizer that is used for the polyvinyl chloride plastic material formula just.
Purpose of the present invention is achieved through the following technical solutions:
A kind of epoxy composite zinc soap thermo-stabilizer that is used for the polyvinyl chloride plastic material formula contains following component and parts by weight: main stabilizer 100, co-stabilizer 1～80, external lubricant 1～140.
Described main stabilizer is the compound zinc soap of epoxy unsaturated high-grade fatty acid, and described co-stabilizer is beta-diketone compound or organic phosphorous acid ester cpds.
The compound zinc soap of above-mentioned epoxy unsaturated high-grade fatty acid is epoxy unsaturated high-grade fatty acid and C
6～C
18Monobasic or binary is saturated or the saponified mixture of zinc metal of unsaturated organic acid; Epoxy unsaturated high-grade fatty acid group and C
6～C
18Monobasic or binary is saturated or the unsaturated organic acid group is formed the saponified mixture of zinc metal with mol ratio 5:5～9:1.Described epoxy unsaturated high-grade fatty acid is selected from epoxyoleic acid, epoxy ricinolic acid; Described C
6～C
18Monobasic or binary is saturated or unsaturated organic acid, be selected from lauric acid, Palmiticacid, stearic acid, 12-oxystearic acid, oleic acid, ricinolic acid, Whitfield's ointment, anthranilic acid, hexanodioic acid, sebacic acid.
Above-mentioned beta-diketone compound is selected from phenyl methyl ketone formyl methane, stearoyl benzoyl methane, diphenylpropane-1,3-dione(DPPO).
Above-mentioned organic phosphorous acid ester cpds is selected from triaryl ester, trialkyl ester, three (alkylated aryl ester), alkylaryl mixed ester, trithio alkyl ester, bis-phosphite, aggretion type phosphorous acid ester.
Above-mentioned external lubricant is selected from polyethylene wax, oxidic polyethylene, polyethylene ionomer, poly-hydrofluoric ether, paraffin, ester type waxes, amide waxe, S wax (C
28～32Higher fatty acid), Fischer-Tropsch synthetic wax, polymeric amide, polyvinyl alcohol.
The epoxy composite zinc soap thermo-stabilizer that is used for the polyvinyl chloride plastic material formula of the present invention also comprises oxidation inhibitor, anionic type laminated material, C
8～C
22Calcium or strontium or magnesium or aluminum metal is saponified, one or more the mixture in the polyol compound, white dyes, its parts by weight are respectively:
Main stabilizer 100
Co-stabilizer 1～80
External lubricant 1～140
Oxidation inhibitor 0～20
Anionic type laminated material 0～30
C
8～C
22Calcium or strontium or magnesium or aluminum metal saponified 0～100
Polyol compound 0～30
White dyes 0～10.
Described oxidation inhibitor is selected from antioxidant 1076, antioxidant 1010, anti-oxidant DLTP, oxidation inhibitor DSTP, oxidation inhibitor ODP, dihydroxyphenyl propane; Described anionic type laminated material is magnalium carbonate type LDH; Described C
8～C
22Calcium or strontium or magnesium or saponified calcium stearate, Magnesium Stearate, strontium stearate, the aluminum stearate of being selected from of aluminum metal; Described polyol compound is selected from dipentaerythritol, tetramethylolmethane; Described white dyes is selected from white dyes PF, fluorescent brightener CBS-127, white dyes OB.
Compared with prior art, the present invention has following beneficial effect:
1, the stable mechanism with epoxy compounds and organic zinc metallic soap combines, and its long-term thermal stability is better than the physical mixed of epoxy compounds and organic zinc metallic soap, can be applied to the melt-processed process of hard product such as PVC plumbing tubing, section bar well;
2, in PVC melt-processed process, has good initial stage form and aspect stability;
3, epoxy composite zinc soap heat stabilizer system has flexibly adjustable oilness, and the concentration that can make lubricant is limited in the incrustation too much in the PVC prescription course of processing and the generation of black particle effectively by balance delicately, improves plant efficiency.
Description of drawings
Fig. 1 is the dynamic thermal stability comparison diagram.
Embodiment
Each component is mixed by weight proportion, can be prepared into polyvinyl-chloride use epoxy composite zinc soap thermo-stabilizer of the present invention, concrete component and the parts by weight of each embodiment are as shown in table 1.
Table 1
Epoxy composite zinc soap thermo-stabilizer and commercially available calcium zinc heat stabilizer resistance toheat test-results such as table 2 and shown in Figure 1 relatively:
Table 2, static heat stability are relatively
Annotate: dry state: 100 parts of PVC, 3.5 parts of thermo-stabilizers, grind mixing, press the test of GB2917-82 A method;
Hygrometric state: 100 parts of PVC, 60 parts of DBP, 3.5 parts of thermo-stabilizers, other are tested with dry state;
Baking oven test: 100 parts of PVC, 40 parts of DBP, 3.5 parts of thermo-stabilizers, miniature high-speed mixing machine mixing, 145 ± 5 ℃ of roller temperature, roll spacing 1mm twin-screw extruder are plasticated in flakes, make 3cm * 3cm test piece, in 180 ± 2 ℃ of baking ovens, timing sampling is observed test piece variable color situation.
Annotate: rheological test: 100 parts of PVC, 3.5 parts of thermo-stabilizers, 5 parts of lime carbonate, 2 parts of titanium dioxides, 4 parts of chlorinatedpolyethylenees, 1 part of ACR, miniature high-speed mixing machine mixing is got test portion 72 grams, and 185 ℃, 30 rev/mins, with the Haake rheometer test.
Test-results shows that heat-stable time, the especially dynamic thermal stability of polyvinyl-chloride use epoxy composite zinc soap thermo-stabilizer of the present invention obviously are better than commercially available thermo-stabilizer; This epoxy composite zinc soap thermo-stabilizer initial stage form and aspect excellent in stability, it is painted in early days that goods are produced; Nontoxic, heavy metal free pollutes, and can be widely used in the nontoxic goods of various PVC useful HUMAN HEALTH and environment protection.
Claims (7)
1. epoxy composite zinc soap thermo-stabilizer that is used for the polyvinyl chloride plastic material formula is characterized in that containing following component and parts by weight:
Main stabilizer 100
Co-stabilizer 1～80
External lubricant 1～140
Described main stabilizer is the compound zinc soap of epoxy unsaturated high-grade fatty acid, and described co-stabilizer is a beta-diketone compound;
The compound zinc soap of described epoxy unsaturated high-grade fatty acid is epoxy unsaturated high-grade fatty acid and C
6～C
18Monobasic or binary is saturated or the saponified mixture of zinc metal of unsaturated organic acid; Epoxy unsaturated high-grade fatty acid group and C
6～C
18Monobasic or binary is saturated or the unsaturated organic acid group is formed the saponified mixture of zinc metal with mol ratio 5:5～9:1;
Described epoxy unsaturated high-grade fatty acid is selected from epoxyoleic acid or epoxy ricinolic acid; Described C
6～C
18Monobasic or binary is saturated or unsaturated organic acid, be selected from lauric acid, Palmiticacid, stearic acid, oleic acid, ricinolic acid, Whitfield's ointment, anthranilic acid, hexanodioic acid or sebacic acid.
2. epoxy composite zinc soap thermo-stabilizer according to claim 1 is characterized in that described beta-diketone compound, is selected from phenyl methyl ketone formyl methane, stearoyl benzoyl methane or diphenylpropane-1,3-dione(DPPO).
3. epoxy composite zinc soap thermo-stabilizer according to claim 1, it is characterized in that described external lubricant, be selected from polyethylene wax, oxidic polyethylene, poly-hydrofluoric ether, paraffin, ester type waxes, amide waxe, S wax, Fischer-Tropsch synthetic wax, polymeric amide or polyvinyl alcohol.
4. epoxy composite zinc soap thermo-stabilizer according to claim 1 is characterized in that described epoxy composite zinc soap thermo-stabilizer also comprises oxidation inhibitor, anionic type laminated material, C
8～C
22Calcium or strontium or magnesium or aluminum metal is saponified, one or more the mixture in the polyol compound, white dyes, its parts by weight are respectively:
Oxidation inhibitor 0～20
Anionic type laminated material 0～30
C
8～C
22Calcium or strontium or magnesium or aluminum metal saponified 0～100
Polyol compound 0～30
White dyes 0～10.
5. epoxy composite zinc soap thermo-stabilizer according to claim 4 is characterized in that described oxidation inhibitor is selected from antioxidant 1076, antioxidant 1010, anti-oxidant DLTP, oxidation inhibitor DSTP, oxidation inhibitor ODP or dihydroxyphenyl propane.
6. epoxy composite zinc soap thermo-stabilizer according to claim 4 is characterized in that described anionic type laminated material is magnalium carbonate type LDH, described C
8～C
22Calcium or strontium or magnesium or saponified calcium stearate, Magnesium Stearate, strontium stearate or the aluminum stearate of being selected from of aluminum metal.
7. epoxy composite zinc soap thermo-stabilizer according to claim 4 is characterized in that described polyol compound is selected from dipentaerythritol or tetramethylolmethane; Described white dyes is selected from white dyes PF, fluorescent brightener CBS-127 or white dyes OB.
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| CNB2005100369695A CN100497467C (en) | 2005-09-02 | 2005-09-02 | Epoxy-zinc soap compound as heat stabilizer for polyvinyl chloride plastic formula |
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| CNB2005100369695A CN100497467C (en) | 2005-09-02 | 2005-09-02 | Epoxy-zinc soap compound as heat stabilizer for polyvinyl chloride plastic formula |
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| CN100497467C true CN100497467C (en) | 2009-06-10 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100469833C (en) * | 2007-02-15 | 2009-03-18 | 宜兴市三联化工厂 | Method of preparing polyvinylchloride composite processing auxiliary agent |
| CN101270204B (en) * | 2007-03-21 | 2010-11-17 | 厦门绿业化工有限公司 | Zincium magnalium solid compound stabilizer and preparation method thereof |
| CN101851161B (en) * | 2010-03-30 | 2013-07-17 | 桐乡市中诚化工有限公司 | Large molecular weight polyalcohol and polyprotic acid organic ester and synthesis method and application thereof |
| CN101967253A (en) * | 2010-10-26 | 2011-02-09 | 湘乡市贝特尔塑胶有限公司 | Environmentally-friendly PVC calcium zinc composite stabilizer |
| CN103131050B (en) * | 2012-07-25 | 2014-10-15 | 肇庆市森德利化工实业有限公司 | Fatty acid calcium zinc composite and preparing method thereof |
| CN102875924A (en) * | 2012-10-12 | 2013-01-16 | 中塑联新材料科技湖北有限公司 | Special stability function regulator for polyvinyl chloride (PVC) artificial leather |
| CN104877257A (en) * | 2015-04-30 | 2015-09-02 | 苏州乔布注塑工业有限公司 | External PVC lubricating agent |
| CN107129598A (en) * | 2017-06-09 | 2017-09-05 | 苏州朗创化工有限公司 | A kind of environmental protection calcium zinc stabilizer for improving electric wire electrical property |
| CN109232975B (en) * | 2018-03-29 | 2020-07-03 | 唐山师范学院 | Liquid calcium-zinc heat stabilizer for PVC (polyvinyl chloride) and preparation method thereof |
| CN111117451A (en) * | 2019-12-06 | 2020-05-08 | 苏州吉人高新材料股份有限公司 | Three-type high-flash-point safe anticorrosive finish paint |
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| CN1583849A (en) * | 2004-06-11 | 2005-02-23 | 广东广洋高科技股份有限公司 | Rare earth and calcium and zinc stabilizer for polychlorovinyl and its preparation |
| CN1618793A (en) * | 2004-10-08 | 2005-05-25 | 广东联塑科技实业有限公司 | Preparation method of epoxy unsaturuted higher futty acid compound zinc soap |
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2005
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583849A (en) * | 2004-06-11 | 2005-02-23 | 广东广洋高科技股份有限公司 | Rare earth and calcium and zinc stabilizer for polychlorovinyl and its preparation |
| CN1618793A (en) * | 2004-10-08 | 2005-05-25 | 广东联塑科技实业有限公司 | Preparation method of epoxy unsaturuted higher futty acid compound zinc soap |
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