CN101671447B - Liquid heat stabilizer special for cable wires - Google Patents
Liquid heat stabilizer special for cable wires Download PDFInfo
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- CN101671447B CN101671447B CN200810120917XA CN200810120917A CN101671447B CN 101671447 B CN101671447 B CN 101671447B CN 200810120917X A CN200810120917X A CN 200810120917XA CN 200810120917 A CN200810120917 A CN 200810120917A CN 101671447 B CN101671447 B CN 101671447B
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Abstract
The invention relates to a liquid heat stabilizer special for cable wires. The formula of the liquid heat stabilizer comprises the following components in portion by weight: 40 to 60 portions of organic liquid single-component substance of calcium metal, 5 to 20 portions of organic liquid single-component substance of zinc metal, 5 to 20 portions of organic liquid single-component substance of magnesium metal, 15 to 40 portions of organic liquid single-component substance of barium metal, 5 to 20 portions of diphenyl thiourea or stearoyl benzene alkyl, 3 to 10 portions of polyalcohol, 20 to 50 portions of phosphite ester, 0.05 to 5 portions of oxadiazoles derivatives, and 1 to 10 portions of amino uracil. The best effect of nitrogen-containing organic substances is the collaborative effect of 6-amino-1, 3-diphenyl uracil, and 2,5-diphenyl-1,3,4-oxadiazoles. The liquid heat stabilizer has the advantages of good collaborative effect of components and good stability and lubricating effect, integrally improves the stability for processing PVC, and can effectively improve the initial tinting of the PVC and solve the foaming problem.
Description
Technical field
The present invention relates to a kind of auxiliary chemicals, especially relate to the heat of liquid stablizer that uses a kind of cable and wire special use.
Background technology
Polyvinyl chloride (PVC) has been widely used in wire cable insulating layer and sheath.The fast development of the transformation of China's power network, automotive industry, communication industry, all the development for electric wire, cable enterprise provides unprecedented opportunities.But adopt the PVC CABLE MATERIALS or the hazardous and noxious substances of traditional hot stablizer to exceed standard, do not reach environmental requirement, or reached environmental requirement, but the thermostability of goods own is low, electrical insulating property is poor.PVC is subjected to heat, mechanical shear stress in processing and use, the influence of oxygen and light, being easy to degraded destroys---and early stage, the The apparent phenomenon of degraded was exactly variable color, finally had influence on the outward appearance work-ing life of goods, therefore must use thermo-stabilizer in the PVC course of processing.Along with the progress of science and technology and the continuous upgrading of environmental requirement, the technical need of thermo-stabilizer aspect environmental protection becomes increasingly conspicuous.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.At present on American-European market, be seen in report, be in calcium/zinc product, to add itrogenous organic substance, as amino uracil, reach the environmental requirement of unleaded heavy metal free, a kind of liquid stabilisers based on the metallic soap system is disclosed among Chinese patent " special-purpose metal organic salt monomer for liquid stabilizer and preparation method thereof " (application number CN200610154753.3) and " a kind of double matching type heat stabilizer " (application number CN200710069728.X), after in this liquid stabilisers system, having added amino uracil, discover that amino uracil is undesirable to the stabilizing effect that improves PVC, especially limited to the stabilizing effect that improves the suitable PVC material of cable and wire, and cause the painted or foaming of stabilising system easily, thereby reduce the overall performance of PVC cable and wire goods.
Summary of the invention
One of purpose of the present invention is the heat of liquid stablizer of a kind of cable and wire special use of research, solve in the preparation process of PVC cable and wire material, amino uracil causes the painted or blistered problem of stabilising system, an object of the present invention is to filter out the itrogenous organic substance that is applicable to metallic soap system liquid stabilisers, the stability of thus obtained PVC cable and wire goods is comparatively desirable.
Above-mentioned purpose of the present invention mainly is achieved by following technical proposals: the heat of liquid stablizer of cable and wire special use is based on metallic soap class I liquid I thermo-stabilizer, and has added itrogenous organic substance; The mixture of described itrogenous organic substance Wei oxadiazole derivative or amino uracil, Huo oxadiazole derivative and uridylic; Described metallic soap class system is a liquid, is the monomeric compound system of metallic soap that makes after any one and lipid acid, monohydric phenol, the higher alcohols reaction of calcium, zinc, magnesium, barium, strontium; The prescription of described heat of liquid stablizer 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, diphenyl thiourea or stearyl benzene alkane 5～20, polyvalent alcohol 3～10, phosphorous acid ester 20～50, oxadiazole derivatives 0.05～5, amino uracil 1～10.
As preferably, described amino uracil preferably has the 6-amino-1 of following molecular formula, 3-phenylbenzene uridylic:
As preferably, 2,5-phenylbenzene that Suo Shu oxadiazole derivative preferably has following molecular formula, 1,3,4 — oxadiazoles:
Wherein :-R1 and R2 are carboxyl, aryl, alkyl, hydroxyl or hydroxyl oxygen base;
As preferably, described metallic soap system has also been added the metallic soap monomer that makes after 3～5 parts of tin and lipid acid, monohydric phenol, the higher alcohols reactions.
As preferably, the metallic soap system has also been added the metallic soap monomer that makes after 3～5 parts of cadmiums and lipid acid, monohydric phenol, the higher alcohols reactions.
As preferably, the preferred 6-amino-1 of described amino uracil, 3-phenylbenzene uridylic.
As preferably, based on the weight of liquid stabilisers, 2,5-phenylbenzene, the preferred 0.5%-5% of the weight percent of 1,3,4 — oxadiazoles, 6-amino-1, the preferred 5%-10% of 3-phenylbenzene uridylic.
The mechanism of action of nitrogenous organic stable material:
The inventor finds that in research and process of the test ， oxadiazole derivative can promote the stability of amino uracil to PVC processing, improves the initial coloration of PVC.In fact, there is good promoter action between this compound of two types.
You Yu oxadiazole derivative and amino uracil have heterocycle, and metal ion is had the good adsorption ability, can utilize heteroatoms and metal ion in the ring to form stable multiple tooth title complex, and the metal-chelating reaction is:
Because two easy adsorbing metal ions of phenyl delocalized πDian Zi can obviously strengthen chelated mineral to the heterocyclic internal divergence, make the more function group play effect.In the presence of calcium stearate/zinc, carbon-alkoxylation displacement chlorallylene atom can take place in organic stable material and metal-chelating.With the cancellation from the PVC macromolecular main chain of unsettled chlorine atom, this is a kind of of paramount importance stabilization reactions, replaces process reaction and is:
Nitrogenous organic stable material such as amino uracil, dihydrogen pyridine derivative (ester, ester amine or amine), can well neutralize absorbs PVC because of the HCl that thermal destruction discharges, and plays and suppresses PVC thermolysis effect, and the reaction process that absorbs HCl is as follows:
Amino uracil directly absorbs HCl, and this is to add amino uridylic than simple 2, the 5-phenylbenzene that is suitable for, the good reason of 1,3,4 — oxadiazole stabilising effects, it absorbs the HCl water generation reaction unlike lead salt again, does not give PVC internal structure generation acid solvent and impels the PVC accelerated deterioration.
Under normal conditions, oxygen in the PVC processing environment can't be got rid of, the free radical (P) that generates in airborne oxygen and the PVC thermal degradation process forms peroxylradicals (POO), the reactive hydrogen that POO captures among the PVC forms new free radical (P) and hydroperoxide (POOH), POOH decomposes alkoxy free group (PO) and the hydroxyl radical free radical (OH) that produces, and can quicken the oxidative degradation of PVC.Nitrogenous organic stable material can be caught POO rapidly and be generated POOH, plays the thermooxidizing stabilization of PVC.The reaction process that nitrogenous organic stable material is caught POO generation POOH is as follows:
Therefore, the present invention has the prescription science, and each component acts synergistically, and integral body has improved the stability to PVC processing, can effectively improve the initial coloration of PVC, solves the foaming problem, plays extraordinary thermostable effect in CABLE MATERIALS processing.Can reach eliminate activity chlorine, absorb PVC and deviate from HCl, decompose hydroperoxide and organize effect such as autoxidation.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1: in parts by weight, get 20 parts of 50 parts of calcium carboxylates, 8 parts of zinc carboxylates, 5 parts of magnesium carboxylates, 15 parts of carboxylic acid barium, 5 parts of diphenyl thioureas, 7 parts of Sorbitol Powders, phosphorous acid ester, 2 respectively, 5-phenylbenzene, 1,3,0.2 part of 4 — oxadiazole, 6-amino-1,2 parts of 3-phenylbenzene uridylics, composite forming.
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, or 5～20, phosphorous acid ester 5～8 oxadiazole derivatives 0.05～5, amino uracil 1～10.
Embodiment 2: in parts by weight, get 25 parts of calcium carboxylates respectively, 25 parts of zinc carboxylates, 5 parts of magnesium carboxylates, 25 parts of carboxylic acid barium, 8 parts in stearyl benzene alkane, 3 parts of tetramethylolmethanes, 30 parts of phosphorous acid esters, 2,5-phenylbenzene, 0.5 part of 1,3,4 — oxadiazole, 6-amino-1,4 parts of 3-phenylbenzene uridylics, composite forming.
Embodiment 3: in parts by weight, get 25 parts of calcium carboxylates respectively, 25 parts of zinc carboxylates, 5 parts of magnesium carboxylates, 25 parts of carboxylic acid barium, 3 parts of carboxylic acid cadmiums, 8 parts in stearyl benzene alkane, 3 parts of tetramethylolmethanes, 30 parts of phosphorous acid esters, 2,5-phenylbenzene, 1,3,0.5 part of 4 — oxadiazole, 6-amino-1,4 parts of 3-phenylbenzene uridylics, 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 (6)
1. the heat of liquid stablizer of a cable and wire special use, it is characterized in that described heat of liquid stablizer is the metallic soap class system of having added itrogenous organic substance, described itrogenous organic substance Wei oxadiazole derivative and amino uracil, the structural formula of Suo Shu De oxadiazole derivative is as follows:
Wherein :-R
1And R
2Be carboxyl, aryl, alkyl, hydroxyl or hydroxyl oxygen base;
Described metallic soap class system is a liquid, is the monomeric compound system of metallic soap that makes after any one and lipid acid, monohydric phenol, the higher alcohols reaction of calcium, zinc, magnesium, barium, strontium.
2. the heat of liquid stablizer of a kind of cable and wire special use according to claim 1, the prescription that it is characterized in that described heat of liquid stablizer is: in parts by weight, and 40～60 parts of the organic liquid single component materials of calcium metal, 5～20 parts of the organic liquid single component materials of zinc metal, 5～20 parts of the organic liquid single component materials of magnesium metal, 15～40 parts of the organic liquid single component materials of barium metal, 5～20 parts of diphenyl thiourea or stearoyl benzoyl methanes, 3～10 parts of polyvalent alcohols, 0.05～5 part in 20～50 parts of oxadiazoles of phosphorous acid ester derivative, 1～10 part of amino uracil.
3. according to the heat of liquid stablizer of a kind of cable and wire special use of claim 1 or 2, it is characterized in that: a: described amino uracil is the 6-amino-1 with following molecular formula, 3-phenylbenzene uridylic:
4. according to the heat of liquid stablizer of a kind of cable and wire special use of claim 1 or 2, it is characterized in that described metallic soap system also added the metallic soap monomer that makes after 3～5 parts of tin and lipid acid, monohydric phenol, the higher alcohols reaction.
5. according to the heat of liquid stablizer of a kind of cable and wire special use of claim 1 or 2, it is characterized in that described metallic soap system also added the metallic soap monomer that makes after 3～5 parts of cadmiums and lipid acid, monohydric phenol, the higher alcohols reaction.
6. the heat of liquid stablizer of a kind of cable and wire special use according to claim 3 is characterized in that: based on the parts by weight of liquid stabilisers, and 2,5-phenylbenzene-1,3,4-oxadiazole are 0.5～5 part, 6-amino-1,3-phenylbenzene uridylic is 5～10 parts.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810120917XA CN101671447B (en) | 2008-09-11 | 2008-09-11 | Liquid heat stabilizer special for cable wires |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810120917XA CN101671447B (en) | 2008-09-11 | 2008-09-11 | Liquid heat stabilizer special for cable wires |
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| CN101671447A CN101671447A (en) | 2010-03-17 |
| CN101671447B true CN101671447B (en) | 2011-11-23 |
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| CN200810120917XA Expired - Fee Related CN101671447B (en) | 2008-09-11 | 2008-09-11 | Liquid heat stabilizer special for cable wires |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103665635B (en) * | 2013-11-25 | 2015-10-21 | 安徽师范大学 | A kind of electric wire non-toxic stabilizer |
| CN113773552A (en) * | 2021-09-27 | 2021-12-10 | 山东慧科助剂股份有限公司 | Dihydropyridine PVC composite heat stabilizer and preparation method thereof |
Citations (5)
| 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 |
| CN1489614A (en) * | 2001-02-16 | 2004-04-14 | ����ķ�ն���ϩ��Ӽ�����˾ | Halogen-contained polymer stabilizing novel stabilizer system |
| CN1536015A (en) * | 2003-04-10 | 2004-10-13 | 深圳市海川实业股份有限公司 | Composite thermal stabilizing agent for polyvinyl chloride and its derivative composition |
| CN101092492A (en) * | 2007-06-26 | 2007-12-26 | 杭州新新塑料助剂科研有限公司 | Double matching type heat stabilizer |
-
2008
- 2008-09-11 CN CN200810120917XA patent/CN101671447B/en not_active Expired - Fee Related
Patent Citations (5)
| 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 |
| CN1489614A (en) * | 2001-02-16 | 2004-04-14 | ����ķ�ն���ϩ��Ӽ�����˾ | Halogen-contained polymer stabilizing novel stabilizer system |
| CN1536015A (en) * | 2003-04-10 | 2004-10-13 | 深圳市海川实业股份有限公司 | Composite thermal stabilizing agent for polyvinyl chloride and its derivative composition |
| CN101092492A (en) * | 2007-06-26 | 2007-12-26 | 杭州新新塑料助剂科研有限公司 | Double matching type heat stabilizer |
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Owner name: HANGZHOU SANYE NEW MATERIAL CO., LTD. Free format text: FORMER OWNER: HANGZHOU XINXIN PLASTICS AUXILIARY TECHNOLOGY CO., LTD. Effective date: 20100723 |
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Effective date of registration: 20100723 Address after: 310000 No. 20 Cai Ma Dong Road, Hangzhou, Zhejiang, Gongshu District Applicant after: Hangzhou Sanye New Materials Co., Ltd. Address before: 310000 No. 20 Cai Ma Dong Road, Hangzhou, Zhejiang, Gongshu District Applicant before: Hangzhou Xinxin Plastics Auxiliary Technology Co., Ltd. |
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Granted publication date: 20111123 Termination date: 20170911 |