CN100564435C - A kind of double matching type heat stabilizer - Google Patents
A kind of double matching type heat stabilizer Download PDFInfo
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- CN100564435C CN100564435C CNB200710069728XA CN200710069728A CN100564435C CN 100564435 C CN100564435 C CN 100564435C CN B200710069728X A CNB200710069728X A CN B200710069728XA CN 200710069728 A CN200710069728 A CN 200710069728A CN 100564435 C CN100564435 C CN 100564435C
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Abstract
The present invention relates to the double matching type heat stabilizer that a kind of PVC CABLE MATERIALS is suitable for.The prescription of thermo-stabilizer is: in parts by weight, the organic liquid single component material 5～20 of the organic liquid single component material 40～60 of calcium metal, the organic liquid single component material 5～20 of zinc metal, magnesium metal, the organic liquid single component material 15～40 of barium metal, organic stabilizer 5～20, Synergistic stabilizer 5～8; Wherein said organic stabilizer is diphenyl thiourea or stearyl benzene alkane, described Synergistic stabilizer is the phosphorous acid esters materials, has reasonable recipe, method is easy, to PVC goods Heat stability is good, characteristics such as excellent property, production cost are low are suitable for and apply.
Description
Technical field
The present invention relates to a kind of auxiliary chemicals, especially relate to the double matching type heat stabilizer that a kind of PVC CABLE MATERIALS is suitable for.
Background technology
The environment-friendly stabilizer of China also is in development at present, most of commercial calcium, the agent of zinc Pickering all are simple mixing such as calcium stearate, Zinic stearas, Aluminum Carbonate Basic, magnesium (give and claim hydrotalcite), beta-diketon, more than each component all be common, the traditional commodities product of outsourcing, there is no that new technology, novel material occur, maximum defective has portioned product also to add lead composition (all be certainly be controlled at limit the quantity of in); And the calcium of liquid, zinc product is the technology of 1980's basically, all use 2 ethyl hexanoic acid, oleic acid, organic carboxyl acids such as phenylformic acid are made raw material and are adopted traditional saponification-multiple anti-technology or direct hydrogenation technology and calcium separated, magnesium, the zinc reaction generates single component and adds Phenyl Di-2-ethyl Hexyl Phosphite, epoxy soybean oil, beta-diketons etc. are composite to form, this series products metal content is low, calcium≤6% wherein, zinc≤12%, magnesium≤5%, barium≤16%, cause thermally-stabilised effect extreme difference, it is all undesirable to performances such as its well-illuminated degree to be used for the PVC plastics, and since CABLE MATERIALS to volume specific resistance, 200 ℃ of Congo red detections, copper core oxidation etc. has very strict requirement, so up to now, the heat of liquid stablizer that has report to use is not seen in the whole world in the processing of PVC CABLE MATERIALS.
The U.S., Japan, Europe begin research and development to the environment-friendly type thermo-stabilizer as far back as the sixties in last century, having a large amount of research papers and the patent researched and developed at mistake base calcium, zinc, barium to the seventies sends out, as U.S. Patent number be: 2.616,904,2.767,164,2.798,852,3.027,325,3.031,28k etc.But these patented technologies have same problem when implementing: the one, and technology is numerous and diverse excessively, the extremely difficult control of operation skill; The 2nd, though can prepare high-content, highly purified single component, cost is too high, can't carry out industrializing implementation, does not therefore have actual use value.
Summary of the invention
The objective of the invention is to solve the problems referred to above that thermo-stabilizer exists, provide a kind of cost moderate, technology is easy, the liquid stabilisers of Heat stability is good.
Above-mentioned purpose of the present invention is achieved through the following technical solutions: the prescription of thermo-stabilizer is: in parts by weight, the organic liquid single component material 5～20 of the organic liquid single component material 40～60 of calcium metal, the organic liquid single component material 5～20 of zinc metal, magnesium metal, the organic liquid single component material 15～40 of barium metal, organic stabilizer 5～20, Synergistic stabilizer 5～8; Wherein said organic stabilizer is diphenyl thiourea or stearyl benzene alkane, and described Synergistic stabilizer is the phosphorous acid esters materials.
Described organic liquid single component material is the mixture of the organic salt of calcium, zinc, magnesium, barium metal, and organic salt was meant the alkali carboxylate salt, crosses alkali carbonate, crosses alkali phenates any one or mixture here.The content of calcium metal is 4%～12% in the organic liquid single component material of described calcium metal; The content of zinc metal is 10%～20% in the organic liquid single component material of described zinc metal; The content of magnesium metal is 4%～12% in the organic liquid single component material of described magnesium metal; The content of barium metal is 28%～50% in the organic liquid single component material of described barium metal.
As preferably, described organic stabilizer also can be stearyl-benzoyl-methane or beta-amino crotonate;
As preferably, described Synergistic stabilizer also can be the epoxy compounds that comprises epoxy soybean oil, appropriate youngster's fatty acid oil, or any one of polyvalent alcohol and dihydropyridine, β-Yang Hua carboxylicesters, 1-3-diketone, trihydroxy methyl propane.
Theoretical foundation of the present invention is:
The metal that can relate in the PVC goods processing technology, we can be divided into two big class, i.e. Cd, Zn class and Ba, Ca, Mg classes according to the stabilization function of metallic compound.The major function of Cd compound and Zn compound is: (1) catches the HCL that PVC discharges, thereby PVC is had effect steady in a long-term; (2) Cd compound and Zn compound make PVC stable by the growth of displacement chlorallylene inhibition polyenoid chain.Ba, Ca, Mg class can be caught the HCl that PVC discharges equally, but can not replace chlorallylene, therefore, when they use separately, lack the ability that stops the polyenoid chain to be grown up, and can not suppress initial coloration.The stable mechanism of two big metal compounds has nothing in common with each other, if they are used, but show synergistic then increases substantially usefulness, reaches the thermostable effect good to PVC.The character of Mg compound very similar to the Ca compound (initial coloring is serious, but long-term thermal stability is better), and Al compound very similar to the Zn compound (good initial stage form and aspect and serious " zinc burning " phenomenon); Mg, Ca, Ba all belongs to second main group element in the period of element, their similar performances, good understanding, but Al is the 3rd main group element, and Zn, Cd is second subgroup element, why very similar is their chemical property? certainly there is the diagonal lines principle that this phenomenon can be described in the periodic law of elements, but the inventor thinks the similarities and differences of element chemistry character, its basic reason is the similarities and differences of its atomic structure, its external sign is that proton is to the bundle of the out-shell electron power similarities and differences of fighting in the nucleus, and this otherness is very complicated, but the easiest be the electronegativity of comparison element like nearly method, be listed as the electronegativity of some elements below, as shown in table 1:
The electronegativity of some elements of table 1
| Element | Mg | Ca | Ba | Zn | Cd | Al | Pb | Sn | Sb |
| Electronegativity | 1.2 3 | 1.0 4 | 0.9 7 | 1.6 6 | 1.4 6 | 1.4 7 | 1.5 5 | 1.7 2 | 1.8 2 |
As seen from the above table, the second main group element Mg is smaller and very approaching to the electronegativity of Ba, illustrate that they attract electronic capability approximate and more weak, they can not form coordinate bond with unstable chlorine atom in the polyvinyl chloride resin (Cl Θ), thereby thereby can not make the negatively charged ion of metallic soap replace the unstable chlorine atom to make PVC take off HCl and form two keys; After the PVC system had a considerable amount of HCl, they can only absorb HCl, thus their organic acid salt as thermo-stabilizer, initial coloration is heavier; And the electronegativity of Zn, Cd, Al, Pb, Sn, Sb big (big approximately more than 50%) attraction electronic capability is stronger, can form coordinate bond with unstable chlorine atom in the polyvinyl chloride resin, thereby can make the negatively charged ion of metallic soap replace the unstable chlorine atom, can prevent PVC decomposing H Cl to form two key reactions, so their organic acid salt all has initial stage form and aspect preferably as thermo-stabilizer, the size that the ability of key is joined in the corresponding carbon atom formation of unstable chlorine atom among certain above-mentioned organic cation and the PVC also influences initial coloring.
Modern quantum chemistry is pointed out: the Zn atom has 4p6 vacant level, the Al atom has 3p5 vacant level, Cd has 5p6 vacant level, Pb has 6p4 vacant level, Sn has 5p4 vacant level, the ion of these elements (heat, light, polar compound inductive effect etc.) under external force can form the sp hybridized orbital, can combine the unstable chlorine atom with corresponding carbon atom and form coordinate bond, the negatively charged ion of stablizer and then replacement unstable chlorine atom, prevention PVC is two keys because of decomposing H Cl forms, so be that cationic thermo-stabilizer initial coloration is all more shallow mutually with these atoms.
Learn that thus the product that the metal of second subgroup element processes all has fabulous thermally-stabilised effect, but because environmental protection requirement, the heavy metals such as outer Pb, Cd that dezincify are all being prohibited the row that (limit) used.For making stablizer can keep good thermal stability, the transparency can meet environmental protection requirement again, have only selection to obtain the generally acknowledged metal that reaches environmental requirement of global industry and come component design with Ca, Zn, Mg etc.And for overcome Ca, Zn, Ba (in the scope of a small amount of environmental regulation permission) wait metal can not replace propyl chloride can't with shortcomings such as chlorine atom (ClO) formation coordination thereby initial coloration difference, the inventor has added organic class material (being called for short OBS) simultaneously in order to improve thermally-stabilised effect and to satisfy the special electrical property of PVC wire cable material in prescription, chemistry, physics, mechanical property, final stablizer be by cross alkali Ca, Zn, Mg, Ba carboxylic acid, cross alkali Ca, Zn, Mg, Ba carbonic acid, cross alkali Ca, Zn, Mg, the Ba phenates is composite forms.
Therefore, the present invention has reasonable recipe, method is easy, and to PVC goods Heat stability is good, characteristics such as excellent property, production cost are low are suitable for and apply.
Embodiment
Below by embodiment, and in conjunction with the accompanying drawings, technical scheme of the present invention is described in further detail.
Embodiment 1: in parts by weight, get 45 parts of two (right-nonyl phenol calcium) respectively, 15 parts of two (right-nonyl phenol zinc), magnesium carboxylates 10.0%, 15 parts of barium carbonates, 5 parts of amino uracils, 5 parts of tetramethylolmethanes, 5 parts of phosphorous acid benzene di-isooctyls, composite forming.
Embodiment 2: in parts by weight, get 50 parts of two (right-nonyl phenol calcium) respectively, 5 parts of two (right-nonyl phenol zinc), 10 parts of magnesium carboxylates, 15 parts of barium carbonates, 5 parts of amino uracils, 5 parts of diphenyl thioureas, 10 parts of phosphorous acid benzene di-isooctyls, composite forming.
At last, should be pointed out that above embodiment only is the more representational example of the present invention.Obviously, technical scheme of the present invention is not limited to the foregoing description, and many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (2)
1. double matching type heat stabilizer, the prescription that it is characterized in that described thermo-stabilizer is: in parts by weight, and the organic liquid single component material 40～60 of calcium metal, the organic liquid single component material 5～20 of zinc metal, the organic liquid single component material 5～20 of magnesium metal, the organic liquid single component material 15～40 of barium metal, organic stabilizer 5～20, Synergistic stabilizer 5～8; The content of calcium metal is 4% in the organic liquid single component material of described calcium metal, the content of zinc metal is 10% in the organic liquid single component material of described zinc metal, the content of magnesium metal is 4% in the organic liquid single component material of described magnesium metal, and the content of barium metal is 28% in the organic liquid single component material of described barium metal; Described organic stabilizer is diphenyl thiourea, stearyl benzene alkane or stearyl-benzoyl-methane, and described Synergistic stabilizer is any one in phosphorous acid esters material, polyvalent alcohol, dihydropyridine, β-Yang Hua carboxylicesters and the 1-3-diketone.
2. a kind of double matching type heat stabilizer according to claim 1 is characterized in that: the organic liquid single component material of described calcium metal is crossing the alkali carboxylate salt, cross alkali carbonate, crossing alkali phenates any one or mixture of calcium metal; The organic liquid single component material of described zinc metal is crossing the alkali carboxylate salt, cross alkali carbonate, crossing alkali phenates any one or mixture of zinc metal; The organic liquid single component material of described magnesium metal is crossing the alkali carboxylate salt, cross alkali carbonate, crossing alkali phenates any one or mixture of magnesium metal; The organic liquid single component material of described barium metal is crossing the alkali carboxylate salt, cross alkali carbonate, crossing alkali phenates any one or mixture of barium metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CNB200710069728XA CN100564435C (en) | 2007-06-26 | 2007-06-26 | A kind of double matching type heat stabilizer |
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| CNB200710069728XA CN100564435C (en) | 2007-06-26 | 2007-06-26 | A kind of double matching type heat stabilizer |
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| CN101092492A CN101092492A (en) | 2007-12-26 |
| CN100564435C true CN100564435C (en) | 2009-12-02 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101289552B (en) * | 2008-06-13 | 2011-12-28 | 肇庆市森德利化工实业有限公司 | Magnesium- aluminum-zinc composition for preparing magnesium- aluminum-zinc composite stabilizer and method of making the same |
| CN101671447B (en) * | 2008-09-11 | 2011-11-23 | 杭州三叶新材料股份有限公司 | Liquid heat stabilizer special for cable wires |
| CN101747529B (en) * | 2009-12-16 | 2011-09-21 | 杭州三叶新材料股份有限公司 | Ca-Zn liquid composite stabilizing agent and application thereof |
| CN101747530B (en) * | 2009-12-16 | 2011-09-21 | 杭州三叶新材料股份有限公司 | Barium-zinc liquid compound stabilizer and application thereof |
| CN102516602B (en) * | 2011-11-29 | 2013-06-19 | 浙江传化华洋化工有限公司 | Method for preparing light excessive alkaline-earth metal alkyl phenate |
| CN103665635B (en) * | 2013-11-25 | 2015-10-21 | 安徽师范大学 | A kind of electric wire non-toxic stabilizer |
| CN105670185B (en) * | 2016-04-19 | 2017-11-10 | 浙江荣远科技有限公司 | A kind of heat-resistant PVC |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4252698A (en) * | 1978-04-17 | 1981-02-24 | Argus Chemical Corporation | Anti-yellowing composition |
| US4665117A (en) * | 1985-12-20 | 1987-05-12 | The Lubrizol Corporation | Basic metal salts having improved color and stability and vinyl halide polymers containing same |
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2007
- 2007-06-26 CN CNB200710069728XA patent/CN100564435C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4252698A (en) * | 1978-04-17 | 1981-02-24 | Argus Chemical Corporation | Anti-yellowing composition |
| US4665117A (en) * | 1985-12-20 | 1987-05-12 | The Lubrizol Corporation | Basic metal salts having improved color and stability and vinyl halide polymers containing same |
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Effective date of registration: 20090220 Address after: 20, Cai Ma Dong Road, Zhejiang, Hangzhou, Gongshu District, China: 310000 Applicant after: Hangzhou Sanye Promoter Co., Ltd. Address before: 20, Cai Ma Dong Road, Zhejiang, Hangzhou, Gongshu District, China: 310000 Applicant before: Hangzhou Xinxin Plastics Auxiliary Technology Co., Ltd. |
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