CN109608785B - Anti-aging PVC composition and preparation method and application thereof - Google Patents
Anti-aging PVC composition and preparation method and application thereof Download PDFInfo
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- CN109608785B CN109608785B CN201811424451.2A CN201811424451A CN109608785B CN 109608785 B CN109608785 B CN 109608785B CN 201811424451 A CN201811424451 A CN 201811424451A CN 109608785 B CN109608785 B CN 109608785B
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- 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
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- 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
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- 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
- C08K5/07—Aldehydes; Ketones
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- 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
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
- C08K5/57—Organo-tin compounds
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
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Abstract
The invention discloses an anti-aging PVC composition, which comprises PVC resin, 10-80 wt% of plasticizer, 1-10 wt% of organic tin heat stabilizer and 0.1-5 wt% of anti-aging auxiliary agent, wherein the weight percentage of the PVC resin is calculated by the weight percentage of the PVC resin, and the anti-aging auxiliary agent is a compound of oxamide auxiliary agent and higher aliphatic ketone auxiliary agent.
Description
Technical Field
The invention belongs to the field of polymer blending and molding processing, and particularly relates to an anti-aging PVC composition and a preparation method thereof, and a product containing the PVC composition.
Background
With the rapid development of video and audio technologies, video cables and audio cables are more and more widely used. Since the arrangement of the wires of the video cable and the audio cable is complicated, in order to ensure the quality of the cable product, a transparent coating layer is generally used to visually observe the arrangement of the wires, for example, the tightness of the arrangement. Therefore, transparent wire coating materials are widely used for video cables and audio cables. Due to the advantages of high cost performance, good transparency, easy processing, light weight and the like, polyvinyl chloride (PVC) materials are widely applied to the coating layers of video cables and audio cables. However, the PVC transparent cable coating material in the current market has the disadvantages of poor transparency, easy aging (e.g., yellowing) of the product, and the like, and the performance of the video cable and the audio cable is seriously affected.
In CN103146096, an anti-aging transparent PVC cable material is prepared from PVC resin, a transparent calcium zinc stabilizer, a plasticizer, a lubricant, a whitening agent, a yellow-eliminating agent and an antioxidant. Compared with the PVC cable coating material adopting the organic tin stabilizer, the PVC cable coating material adopting the transparent calcium zinc stabilizer has poor transparency. The yellowing inhibitor selected in CN103146096 is ultramarine blue powder, the transparency and the brightness of a cable product are easily reduced by adding ultramarine blue, and the yellowing of a PVC cable is deepened along with the prolonging of time.
In CN201711002546, a high-transparent and bright PVC cable material is prepared by using PVC resin, plasticizer, calcium zinc stabilizer, optical interface agent, and optical diffuser. The product has high transparency and low haze, and the optical interface agent and the optical diffusant can improve the transparency and the surface brightness of the product to a certain extent, but the calcium-zinc stabilizer has limited stabilizing effect, so the aging performance of the product is poor, and the product is easy to yellow after long-term use.
Therefore, the existing PVC transparent cable coating material still has the defects of poor transparency and/or easy yellowing of products and the like. Therefore, the development of a PVC cable covering material with high transparency and high aging resistance is very necessary.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an anti-aging PVC composition which has high transparency and high anti-aging property when being used as a cable coating material, and solves the problems that the PVC transparent cable coating material in the prior art has poor transparency and/or the product is easy to yellow and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an ageing-resistant PVC composition, which comprises a PVC resin and 10-80 wt%, preferably 40-60 wt% of a plasticizer in percentage by weight of the PVC resin; 1-10 wt%, preferably 2-8 wt% of an organotin-based heat stabilizer, based on the weight percentage of the PVC resin; and 0.1-5 wt%, preferably 0.5-2 wt% of anti-aging auxiliary agent calculated by the weight percentage of the PVC resin, wherein the anti-aging auxiliary agent is a compound of an oxamide auxiliary agent and a higher aliphatic ketone auxiliary agent.
In some preferred embodiments of the present invention, in the anti-aging auxiliary according to the present invention, the weight ratio of the oxamide auxiliary to the higher aliphatic ketone auxiliary is 3:1 to 6:1, preferably 4:1 to 5:1, such as 3:1, 4:1, 5:1 or 6: 1.
In some preferred embodiments of the invention, the oxalamides of the adjuvant of the inventionCharacterized by containing in the molecular structure
Groups, preferably having a melting point of less than 200 ℃ and containing in the molecular structure
The group-containing hindered phenol auxiliary and/or hindered amine auxiliary is preferably one having a melting point of less than 200 ℃ and a molecular structure containing
A hindered phenolic coagent of the group. Preferred low melting point oxamide adjuvants will achieve better dispersion in PVC compositions and improve the anti-aging effect of the adjuvants in PVC, and such adjuvants are commercially available under the trade designations, for example Omnistab AN697 from Dacheng Qingdao, TINUVIN312 from BASF Ciba Fine, Irganox GX MD1024 from BASF Ciba Fine.
In some preferred embodiments of the present invention, the higher aliphatic ketone auxiliary agent according to the present invention is an aliphatic ketone having 10 to 16 carbon atoms, preferably one or a combination of two or more of ethyl undecyl ketone, 2-tetradecyl ketone, 3-pentadecanedione, 5-methyl-6-pentadecanone, 8-pentadecanone, 2-pentadecanone, cyclopentadecanone, and 6-hexadecanone, and more preferably one or a combination of two or more of ethyl undecyl ketone, 2-tetradecyl ketone, 3-pentadecanedione, 5-methyl-6-pentadecanone, and 8-pentadecanone. The products are available in various brands on the market at present, and the common brands on the market can be adopted.
The inventor of the invention surprisingly finds that the compound of the oxamide auxiliary agent and the higher fatty ketone auxiliary agent in a certain proportion has a very excellent synergistic effect in the aging-resistant PVC composition, the oxamide auxiliary agent can effectively capture free radicals generated by PVC degradation and inhibit the activity of metal ions, α hydrogen atoms of the fatty ketone can effectively react with HCl generated by PVC degradation, and the aging-resistant effect of the compound of the oxamide auxiliary agent and the higher fatty ketone auxiliary agent in a certain proportion is far better than that of a conventional PVC aging-resistant system.
In some preferred embodiments of the present invention, the PVC resin of the present invention is one or a combination of more than one of PVC resins having a polymerization degree of 600-1800, preferably one or a combination of more than one of PVC resins having a polymerization degree of 800-1300 and more preferably an ethylene process PVC resin having a polymerization degree of 1000. the ethylene process PVC resin is a PVC resin prepared by polymerizing ethylene as a raw material to obtain a vinyl chloride monomer by an ethylene oxychlorination method, and is more suitable for preparing a PVC cable covering material having high aging resistance because the molecular weight of the ethylene process PVC resin is higher, the molecular weight distribution is narrower and the residue of impurities is lower than those of a calcium carbide process PVC resin.
In some preferred embodiments of the present invention, the plasticizer according to the present invention is one or more of a phthalic plasticizer, a fatty acid ester plasticizer, a phosphate ester plasticizer, an epoxy ester plasticizer, a polyester plasticizer, a trimellitate plasticizer, and a polyol ester plasticizer, preferably one or more of a phthalic plasticizer, a phosphate ester plasticizer, and an epoxy ester plasticizer, and more preferably one or more of a phthalic plasticizer, a fatty acid ester plasticizer, a phosphate ester plasticizer, and a polyol ester plasticizer. The plasticizer of the present invention may be used in the ordinary commercial grade.
In some preferred embodiments of the present invention, the organotin-based heat stabilizer of the present invention is one or a combination of two or more of organotin maleates, organotin laurates, and organotin sulfur-containing stabilizers, preferably organotin sulfur-containing stabilizers such as organotin mercaptides, which are available in various commercial designations, such as TM-181FS of Rohm and Haas, SS-218 of Arisaema Hubei, KR-600P of Kary chemical technology, Inc. of Changzhou.
The aging-resistant PVC composition can also be added with a lubricant, and the addition amount of the lubricant is 0.3-2 wt% in terms of the weight percentage of the PVC resin. The lubricant can be one or the combination of more than two of fatty acid ester, stearic acid, amide, olefin and organosilicon lubricant, preferably one or the combination of more than two of stearic acid, olefin and organosilicon lubricant, and further preferably one or the combination of more than two of stearic acid lubricant.
In another aspect of the present invention, there is provided a method for preparing an aging-resistant PVC composition, comprising the steps of:
(1) mixing the components, wherein the mixing time is preferably 10-30min, the mixing temperature is preferably 50-100 ℃, and the rotation speed is preferably 300-1000 r/min;
(2) feeding the mixed raw materials into an extruder for extrusion granulation, wherein the extrusion temperature is 150-.
In yet another aspect of the present invention, an article is provided, which is processed from the transparent PVC composition containing the aging resistant PVC composition or prepared by the preparation method of the present invention, preferably the article is a covering material of a cable, preferably including but not limited to a video cable or an audio cable, such as an audio wire, L ED transparent electronic wire, transparent earphone wire or video connection wire, etc.
Compared with the prior art, the invention has the following beneficial effects:
(1) the aging resistance and the transparency of the transparent PVC composition can be obviously improved by compounding the oxamide type auxiliary agent and the higher aliphatic ketone type auxiliary agent in a certain proportion, and the △ YI of the PVC composition subjected to an aging resistance test is less than or equal to 1;
(2) the PVC composition only adds the organic tin heat stabilizer, but can ensure the high transparency of the cable material.
Detailed Description
The process provided by the present invention is described in further detail below, but the present invention is not limited thereto.
Raw materials
Some of the starting materials used in the following examples or comparative examples are illustrated below:
the PVC resin is ONGROVI L-5064 and ONGROVI L-5070 of Bouss chemical (Bornodchem) of Wanhua Hungary, wherein the polymerization degree of ONGROVI L-5064 is 800, the polymerization degree of ONGROVI L-5070 is 1000, and the polymerization degree of HG-800 and HG-1000 of Hanhua Ningbo Co, wherein the polymerization degree of HG-800 is 800, and the polymerization degree of HG-1000 is 1000.
The plasticizer is o-benzene plasticizer DOP of Korea Aijing chemical Co., Ltd, p-benzene plasticizer DOTP of Taiwan, and citrate plasticizer ATBC of Jiangsu Lei union.
Table 1 main performance indicators of three plasticizers:
| index name | Test standard/method | DOP | DOTP | ATBC |
| Color number (platinum-cobalt) number | GB/T 1664 | 30 | ≤30 | ≤50 |
| Acidity (mg/KOH)% | GB/T 1668 | ≤0.1 | ≤0.07 | ≤0.2 |
| Density (20 ℃ C.) g/cm3 | GB/T 4472 | 0.982-0.988 | 0.981-0.985 | 1.037-1.045 |
| Water content wt% | GB11133 | ≤0.1 | ≤0.1 | ≤0.25 |
| Flash point. C | GB1671 | 196 | 220 | 200 |
| Purity% | GC | ＞99.5 | ＞99 | ≥99 |
The organotin stabilizer is organotin mercaptide stabilizer TM-181FS of Rohm and Haas and mercaptide stabilizer SS-218 of Arisaema Hubei.
The transparent Ca-Zn stabilizer in the comparative examples is the transparent Ca-Zn stabilizer XY-620 of Asahi plastics assistants Co., Ltd, and the GO-331T of Shenzhen Hongdao new materials Co., Ltd.
The hindered phenolic antioxidant in the comparative example was Irganox 1010 from BASF Ciba Fine Chemicals.
The higher aliphatic ketone assistant is ethyl undecyl ketone from Shanghai Mirui chemical technology Co., Ltd, 2-tetradecone from Chengdubeister reagent Co., Ltd, and 8-pentadecanone from Shanghai Latin Biotechnology Ltd.
TABLE 2 Main Performance indices of three higher aliphatic ketones
| Index name | Test standard/method | Ethyl undecyl ketone | 2-tetradecone | 8-pentadecanone |
| Density g/cm3 | GB/T 1668 | 0.827 | 0.827 | 0.787 |
| Boiling point of | GB/T 616 | 152 | 148 | 291 |
| Melting Point C | GB/T 617 | 34 | 33.5 | 43 |
| Flash point. C | GB1671 | 66 | 33 | 110 |
| Purity% | GC | ＞95 | ＞95 | ＞95 |
The oxamide auxiliary agent is Omnistab AN697 of Dacheng Chengni of Qingdao, TINUVIN312 of BASF Ciba Fine chemical engineering and Irganox GX MD1024 of BASF Ciba fine chemical engineering, wherein Omnistab AN697 and Irganox GX MD1024 are hindered phenolic auxiliary agents containing oxamide groups, and TINUVIN312 is a hindered amine auxiliary agent containing oxamide groups.
The lubricant is polyethylene wax of Qingdao Sainuo chemical industry with the trademark of L-110, and stearic acid amide of Sichuan Tianyu oil and fat chemical Co., Ltd with the trademark of L utamid SR.
Preparation method of PVC (polyvinyl chloride) composition
The preparation of the PVC compositions in the following examples is described below:
(1) mixing PVC resin, plasticizer, organic tin heat stabilizer, lubricant (if present), and aging resistant auxiliary agent in a high speed mixer (Zhanghong Du Lang 100L) at 80 deg.C and 700r/min for 15 min;
(2) and (3) granulation: feeding the mixed raw materials into a single-screw extruder (SJ-45X 25) through a feeding device for extrusion granulation, wherein the extrusion temperature is 150-.
Test method
Examples or comparative examplesThe test methods referred to in the examples are illustrated below:
tensile strength and elongation at break tests were performed according to ASTM D412;
light transmittance and haze measurements were performed according to ASTM D1003;
the aging resistance test procedure comprises placing a transparent PVC test piece with length of 12mm, width of 6mm and thickness of 2mm at 85 deg.C under 85% relative humidity for 168 hr, and testing the yellowness index YI change value of △ YI (YI change before and after test) before and after aging by using Huntlab UltraScan VIS color difference meter.
Examples
In the following examples and comparative examples, the formulations for preparing the PVC compositions are used in amounts by weight, specifically shown in tables 3-1 to 3-3, wherein the additives are added in amounts of weight percent based on the PVC resin.
Tables 3-1 to 3-3 show the raw materials and formulations (in which the contents of the respective auxiliaries are in terms of weight percentage of PVC resin) of the respective examples and comparative examples
TABLE 3-1
(Note: blank in the Table indicates that the substance was not added)
TABLE 3-2
(Note: blank in the Table indicates that the substance was not added)
Tables 3 to 3
(Note: blank in the Table indicates that the substance was not added)
Tables 4-1 to 4-3 show the results of the performance tests of the PVC compositions obtained for the respective examples and comparative examples
TABLE 4-1
TABLE 4-2
Tables 4 to 3
The comparison between the examples and the comparative examples shows that the PVC composition of the invention or the PVC composition prepared by the method of the invention has very good physical properties such as transparency, tensile strength, elongation at break and the like and aging resistance, and after aging test of placing for 168 hours under the conditions of 85 ℃ and 85% relative humidity, the △ YI of the product is less than 1, thus meeting the requirements of high-end video and audio transparent wires on coating materials in the market and having very wide application prospect.
The present invention has been described in further detail with reference to the specific embodiments, but it should not be construed that the scope of the present invention is limited to the above examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Claims (27)
1. An anti-aging PVC composition comprises PVC resin, 10-80 wt% of plasticizer, 1-10 wt% of organic tin heat stabilizer and 0.1-5 wt% of anti-aging auxiliary agent, wherein the anti-aging auxiliary agent is a compound of oxamide auxiliary agent and higher aliphatic ketone auxiliary agent;
wherein the oxamide auxiliary agent has a melting point lower than 200 ℃ and a molecular structure containing
A hindered phenolic coagent and/or a hindered amine coagent of the group;
the higher aliphatic ketone auxiliary agent is selected from one or the combination of more than two of aliphatic ketones with 10-16 carbon atoms;
the weight ratio of the oxamide auxiliary agent to the higher aliphatic ketone auxiliary agent is 3:1-6: 1.
2. The aging-resistant PVC composition according to claim 1, wherein the weight ratio of the oxamide type auxiliary agent to the higher aliphatic ketone type auxiliary agent in the aging-resistant auxiliary agent is 4:1 to 5: 1.
3. An ageing-resistant PVC composition according to claim 1 or 2, characterised in that the oxamide adjuvant is a hindered phenol adjuvant having a melting point below 200 ℃.
4. The aging-resistant PVC composition according to claim 1 or 2, wherein the higher aliphatic ketone auxiliary agent is one or a combination of two or more of ethyl undecyl ketone, 2-tetradecone, 3-decadione, 5-methyl-6-pentadecone, 8-pentadecone, 2-pentadecone, cyclopentadecanone and 6-hexadecone.
5. The aging-resistant PVC composition according to claim 4, wherein the higher aliphatic ketone auxiliary agent is one or a combination of two or more of ethyl undecyl ketone, 2-tetradecone, 3-decadione, 5-methyl-6-pentadecone or 8-pentadecone.
6. The weatherable PVC composition of claim 1, wherein said weatherable promoter is present in an amount of 0.5 to 2 wt% based on the weight of said PVC resin.
7. An weathering PVC composition according to claim 1, characterized in that the plasticizer content is 40-60% by weight, calculated as a percentage by weight of the PVC resin.
8. The weatherable PVC composition of claim 1, wherein said organotin-based heat stabilizer is present in an amount of 2 to 8 wt% based on the weight of said PVC resin.
9. The aging-resistant PVC composition according to claim 1, wherein the PVC resin is one or a combination of two or more of PVC resins with a polymerization degree of 600-1800.
10. The aging-resistant PVC composition according to claim 9, wherein the PVC resin is one or a combination of two or more of ethylene-based PVC resins with a polymerization degree of 800-1300.
11. An aging-resistant PVC composition according to claim 1 or 7, wherein the plasticizer is one or a combination of two or more of a phthalic plasticizer, a fatty acid ester plasticizer, a phosphate plasticizer, an epoxy ester plasticizer, a polyester plasticizer, a trimellitate plasticizer, and a polyol ester plasticizer.
12. The aging-resistant PVC composition of claim 11, wherein the plasticizer is one or a combination of two or more of ortho-benzene plasticizer, phosphate plasticizer, and epoxy plasticizer.
13. The weatherable PVC composition of claim 12, wherein the plasticizer is one or a combination of two or more of ortho-benzene plasticizers.
14. The aging-resistant PVC composition according to claim 1 or 8, wherein the organotin-based heat stabilizer is one or a combination of two or more of maleic organotin, lauric organotin and sulfur-containing organotin stabilizers.
15. The weatherable PVC composition of claim 14, wherein the organotin-based heat stabilizer is a sulfur-containing organotin stabilizer.
16. The aging-resistant PVC composition according to claim 1, wherein a lubricant is further added, and the lubricant is added in an amount of 0.3-2 wt% based on the weight of the PVC resin.
17. The weatherable PVC composition of claim 16, wherein said lubricant is added in an amount of 0.5 to 1.5 wt% based on the weight percent of said PVC resin.
18. An ageing-resistant PVC composition according to claim 16 or 17, characterised in that the lubricant is selected from one or a combination of two or more of fatty acid esters, stearates, amides, olefins, silicone based lubricants.
19. The weatherable PVC composition of claim 18, wherein the lubricant is selected from one or a combination of two or more of stearic, olefinic, and silicone based lubricants.
20. An ageing-resistant PVC composition according to claim 19, characterised in that the lubricant is selected from one or a combination of two or more of stearic acid based lubricants.
21. Process for the preparation of an ageing-resistant PVC composition according to any one of claims 1 to 20, characterized in that it comprises the following steps:
(1) mixing the components;
(2) and feeding the mixed raw materials into an extruder for extrusion granulation to prepare granules.
22. The method as claimed in claim 21, wherein the mixing time in step (1) is 10-30min, the mixing temperature is 50-100 ℃, and the rotation speed is 300-.
23. The method as claimed in claim 21, wherein the extrusion temperature in step (2) is 150-.
24. An article of manufacture prepared by processing a composition comprising the weatherable PVC composition of any one of claims 1-20 or the weatherable PVC composition prepared by the method of any one of claims 21-23.
25. The article of claim 24, wherein the article is a covering material for a cable.
26. The article of claim 25, wherein the cable comprises a video cable or an audio cable.
27. The article of claim 26, wherein the cable is an audio cord, an L ED transparent electronic cord, a transparent headphone cord, or a video connection cord.
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| CN201811424451.2A CN109608785B (en) | 2018-11-27 | 2018-11-27 | Anti-aging PVC composition and preparation method and application thereof |
| PCT/CN2018/118499 WO2020107389A1 (en) | 2018-11-27 | 2018-11-30 | Anti-aging pvc composition, preparation method therefor and use thereof |
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| CN114196139B (en) * | 2021-12-27 | 2023-08-18 | 国高材高分子材料产业创新中心有限公司 | PVC matrix atomization standard substance and preparation method thereof |
| CN114316470B (en) * | 2021-12-31 | 2023-03-21 | 无锡市弘远塑业科技有限公司 | Rigidity improving method suitable for high-filling PVC material |
| CN115785588A (en) * | 2022-07-21 | 2023-03-14 | 深圳市好亚通防护用品有限公司 | Permanent static dissipative PVC (polyvinyl chloride) sole material and preparation method thereof |
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| JPH0613539B2 (en) * | 1984-07-04 | 1994-02-23 | 旭電化工業株式会社 | Organic phosphite composition |
| DE4204887A1 (en) * | 1992-02-19 | 1993-08-26 | Neynaber Chemie Gmbh | Bis-fatty alkyl ketone(s) used for lubricants - by adding to moulding materials based on polyvinyl chloride and vinyl] chloride copolymers, for high thermostability |
| CN1213391A (en) * | 1996-11-22 | 1999-04-07 | 三井化学株式会社 | Thermoplastic resin composition and film made from the composition |
| JP5170740B2 (en) * | 2007-11-30 | 2013-03-27 | 株式会社Ａｄｅｋａ | Vinyl chloride resin composition |
| CN105968644A (en) * | 2016-06-26 | 2016-09-28 | 陈旭 | Low-smoke, zero-halogen and environment-friendly flame-retardant PVC (polyvinyl chloride) composite |
| CN108003390B (en) * | 2017-12-05 | 2019-07-05 | 广州市联诺化工科技有限公司 | A kind of compound organo-tin het stabilizer of environment-friendly type and preparation method thereof |
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