CN115594886A - Stabilizer for chlorinated polyethylene for flame-retardant ABS production and preparation method thereof - Google Patents
Stabilizer for chlorinated polyethylene for flame-retardant ABS production and preparation method thereof Download PDFInfo
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- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
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Abstract
The invention is suitable for the technical field of flame-retardant ABS additives and preparation methods thereof, and provides a stabilizer for chlorinated polyethylene for flame-retardant ABS production, wherein the stabilizer comprises the following components in parts by weight: 10-50 parts of 6-amino-1, 3-dimethyluracil, 0-20 parts of dihydropyridine carboxylate, 0-10 parts of odorless phosphite ester, 0-10 parts of dipentaerythritol, 10-50 parts of 4A zeolite, 5-35 parts of hydrotalcite, 1-10 parts of hydrated sodium perchlorate, 5-10 parts of superfine talcum powder and 1-10 parts of antioxidant, so that the flame-retardant ABS resin can react with hydrogen chloride to achieve the effect of absorbing hydrogen chloride and inhibit the further catalytic decomposition of CPE, chlorinated polyethylene such as 6-amino-1, 3-dimethyluracil, dihydropyridine carboxylate and odorless phosphite ester is used for improving the thermal stability of CPE, and the initial whiteness and long-term stability for producing the flame-retardant ABS product are guaranteed.
Description
Technical Field
The invention relates to the technical field of flame-retardant ABS additives and preparation methods thereof, in particular to a stabilizer for chlorinated polyethylene for flame-retardant ABS production and a preparation method thereof.
Background
Chlorinated Polyethylene (CPE) is a random polymer prepared by a powdery high-density polyethylene (HDPE) special material through aqueous phase or hydrochloric acid phase suspension chlorination reaction. Chlorinated Polyethylene (CPE) as a saturated high polymer material is non-toxic and tasteless, has excellent weather resistance, ozone resistance, chemical resistance and aging resistance, and has good oil resistance, flame retardance and coloring performance, and good toughness (flexibility at minus 30 ℃). The chlorinated polyethylene resin has wide application, is not only an excellent impact modifier for PVC plastics, but also an elastomer material with good comprehensive performance, is widely used for products such as wires, cables, rubber tubes, waterproof coiled materials and the like, and has good development prospect.
ABS plastics are terpolymers of acrylonitrile (A) -butadiene (B) -styrene (S). ABS plastics are widely applied to the manufacturing industries of machinery, electricity, textiles, automobiles, airplanes, ships and the like and chemical engineering. With the stricter and stricter requirements on the flame retardant property of various equipment parts such as household appliances, communication and the like, the demand of flame retardant ABS plastics is rapidly increasing. However, ABS has poor flame retardancy, and in practical application, a flame retardant is added to improve the flame retardant effect, but the addition of the flame retardant can reduce the physical properties of ABS, especially the impact properties of products are greatly reduced. In order to make ABS plastics achieve good flame retardant property and maintain good mechanical property and forming processability, a third component, namely a thermoplastic elastomer with polar groups, is often added into a formula system of ABS resin and a brominated flame retardant. The Chlorinated Polyethylene (CPE) has good performance in the aspect of impact modification of products, and meanwhile, as the CPE contains chlorine element, the Chlorinated Polyethylene (CPE) has good flame retardant performance and combustion anti-dripping characteristic, and is matched with appropriate proportion of brominated flame retardants, antimony oxide and the like to be cooperatively applied to ABS, so that the Chlorinated Polyethylene (CPE) becomes an ABS flame retardant material with excellent flame retardant performance and low cost.
The melting temperature of ABS plastic is 217-237 ℃, the thermal decomposition temperature is above 250 ℃, and the molding temperature is generally 200-240 ℃. And the thermal stability time measured by the chlorinated polyethylene Congo red method is as follows: at 165 deg.C for about 12min, dehydrochlorination decomposition and yellowing may occur at a high temperature of over 200 deg.C. Therefore, when the chlorinated polyethylene is used for flame-retardant ABS, calcium stearate, calcium zinc stabilizer, organic tin stabilizer and the like are required to be added to improve the thermal stability of CPE, so that the stability and whiteness of the flame-retardant ABS are improved. However, due to the respective defects, the whiteness of the hard calcium is poor at high temperature, the color change of the common calcium zinc stabilizer occurs for a long time due to insufficient heat resistance, the peculiar smell of the organic tin stabilizer and the like, the problems of color difference, yellowing, black yellow spots and the like of the product frequently occur in the flame retardant grade ABS plastic molding product, and the product quality is seriously influenced.
In view of the above, the prior art is obviously inconvenient and disadvantageous in practical use, and needs to be improved.
Disclosure of Invention
Aiming at the defects, the invention aims to provide a stabilizer for chlorinated polyethylene for producing flame-retardant ABS (acrylonitrile-butadiene-styrene) and a preparation method thereof, aiming at the condition that the prior CPE is used for flame-retardant ABS and the product quality is influenced by using stabilizers such as calcium stearate, calcium zinc stabilizer, organic tin stabilizer and the like.
In order to achieve the aim, the invention provides a stabilizer for chlorinated polyethylene for producing flame-retardant ABS, which comprises the following components in parts by weight: 10 to 50 parts of 6-amino-1, 3-dimethyl uracil, 0 to 20 parts of dihydropyridine carboxylate, 0 to 10 parts of odorless phosphite ester, 0 to 10 parts of dipentaerythritol, 10 to 50 parts of 4A zeolite, 5 to 35 parts of hydrotalcite, 1 to 10 parts of hydrated sodium perchlorate, 5 to 10 parts of superfine talcum powder and 1 to 10 parts of antioxidant.
According to the stabilizer for chlorinated polyethylene for flame-retardant ABS production, the antioxidant is one or a mixture of more than one of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid n-octadecyl ester, tetra [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionic acid ] pentaerythritol ester, tri [2, 4-di-tert-butylphenyl ] phosphite and 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid in any proportion.
The invention also provides a preparation method of the stabilizer for chlorinated polyethylene for producing flame-retardant ABS, which comprises the following steps: the method comprises the following steps: accurately weighing the raw materials according to the formula. Adding talcum powder and hydrated sodium perchlorate into a stirrer, and stirring for 5-8min at 30-40 ℃ to obtain a mixture A; step two: adding an antioxidant, hydrotalcite, 4A zeolite and dipentaerythritol into the mixture A obtained in the first step, and stirring for 5-10min at the temperature of 30-50 ℃ to obtain a mixture B; step three: and (2) adding 6-amino-1, 3-dimethyl uracil, dihydropyridine carboxylate and odorless phosphite into the mixture B obtained in the second step, stirring for 10-15min at the temperature of 30-50 ℃, and cooling to obtain the stabilizer for the chlorinated polyethylene for producing the flame-retardant ABS.
Compared with the prior art, the invention has the beneficial effects that:
the stabilizer for chlorinated polyethylene for producing the flame-retardant ABS disclosed by the invention uses an antioxidant, hydrated sodium perchlorate, hydrotalcite, 4A zeolite and dipentaerythritol, the stabilizer mainly achieves the effect of absorbing hydrogen chloride through reaction with the hydrogen chloride, inhibits further catalytic decomposition of CPE, improves the thermal stability of the CPE by using chlorinated polyethylene such as 6-amino-1, 3-dimethyluracil, dihydropyridine carboxylate, odorless phosphite and the like, and ensures the initial whiteness and long-term stability for producing flame-retardant ABS products.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail below with reference to examples, and it should be understood that the specific examples described herein are only for the purpose of explaining the present invention and are not intended to limit the present invention.
Example 1
The stabilizer for the chlorinated polyethylene for producing the flame-retardant ABS comprises the following components in parts by weight: 15 parts of 6-amino-1, 3-dimethyl uracil, 10 parts of dihydropyridine carboxylate, 4 parts of tasteless phosphite ester, 1 part of dipentaerythritol, 30 parts of 4A zeolite, 10 parts of hydrotalcite, 1 part of hydrated sodium perchlorate, 5 parts of superfine talcum powder and 3 parts of antioxidant, wherein the antioxidant is a mixture of n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate and pentaerythritol tetra- [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] in any proportion.
The stabilizer for chlorinated polyethylene applied to flame-retardant ABS production and the preparation method thereof comprise the following steps:
the method comprises the following steps: accurately weighing the raw materials according to a formula, adding talcum powder and hydrated sodium perchlorate into a stirrer, and stirring for 5min at the temperature of 30 ℃ to obtain a mixture A;
step two: adding an antioxidant, hydrotalcite, 4A zeolite and dipentaerythritol into the mixture A obtained in the first step, and stirring for 8min at 40 ℃ to obtain a mixture B;
step three: and (3) adding 6-amino-1, 3-dimethyluracil, dihydropyridine carboxylate and odorless phosphite into the mixture B obtained in the second step, stirring for 10min at 47 ℃, and cooling to obtain the stabilizer for chlorinated polyethylene for producing flame-retardant ABS.
Example 2
The stabilizer for the chlorinated polyethylene for producing the flame-retardant ABS comprises the following components in parts by weight: 40 parts of 6-amino-1, 3-dimethyl uracil, 5 parts of dihydropyridine carboxylate, 5 parts of tasteless phosphite ester, 3 parts of dipentaerythritol, 40 parts of 4A zeolite, 10 parts of hydrotalcite, 2 parts of hydrated sodium perchlorate, 5 parts of superfine talcum powder and 3 parts of antioxidant, wherein the antioxidant is a mixture of pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] and tris [2, 4-di-tert-butylphenyl ] phosphite in any proportion.
The stabilizer for chlorinated polyethylene applied to flame-retardant ABS production and the preparation method thereof comprise the following steps:
the method comprises the following steps: accurately weighing the raw materials according to a formula, adding talcum powder and hydrated sodium perchlorate into a stirrer, and stirring for 8min at 35 ℃ to obtain a mixture A;
step two: adding an antioxidant, hydrotalcite, 4A zeolite and dipentaerythritol into the mixture A obtained in the first step, and stirring for 8min at 35 ℃ to obtain a mixture B;
step three: and (3) adding 6-amino-1, 3-dimethyl uracil, dihydropyridine carboxylate and odorless phosphite into the mixture B obtained in the second step, stirring for 12min at 50 ℃, and cooling to obtain the stabilizer for the chlorinated polyethylene for producing the flame-retardant ABS.
Example 3
The stabilizer for the chlorinated polyethylene for producing the flame-retardant ABS comprises the following components in parts by weight: 45 parts of 6-amino-1, 3-dimethyl uracil, 15 parts of dihydropyridine carboxylate, 6 parts of tasteless phosphite ester, 5 parts of dipentaerythritol, 50 parts of 4A zeolite, 15 parts of hydrotalcite, 6 parts of hydrated sodium perchlorate, 10 parts of superfine talcum powder and 5 parts of antioxidant, wherein the antioxidant is n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris [2, 4-di-tert-butylphenyl ] phosphite ester and 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid which are mixed according to any proportion.
The stabilizer for chlorinated polyethylene applied to flame-retardant ABS production and the preparation method thereof comprise the following steps:
the method comprises the following steps: accurately weighing the raw materials according to a formula, adding talcum powder and hydrated sodium perchlorate into a stirrer, and stirring for 8min at the temperature of 30 ℃ to obtain a mixture A;
step two: adding an antioxidant, hydrotalcite, 4A zeolite and dipentaerythritol into the mixture A obtained in the first step, and stirring for 8min at 35 ℃ to obtain a mixture B;
step three: and (3) adding 6-amino-1, 3-dimethyluracil, dihydropyridine carboxylate and odorless phosphite into the mixture B obtained in the second step, stirring for 12min at 40 ℃, and cooling to obtain the stabilizer for chlorinated polyethylene for producing flame-retardant ABS.
Example 4
The stabilizer for the chlorinated polyethylene for producing the flame-retardant ABS comprises the following components in parts by weight: 45 parts of 6-amino-1, 3-dimethyl uracil, 2 parts of dihydropyridine carboxylate, 2 parts of tasteless phosphite ester, 3 parts of dipentaerythritol, 30 parts of 4A zeolite, 20 parts of hydrotalcite, 6 parts of hydrated sodium perchlorate, 10 parts of superfine talcum powder and 5 parts of antioxidant, wherein the antioxidant is n-octadecyl beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], tris [2, 4-di-tert-butylphenyl ] phosphite or 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid, and one or a mixture of more than one of the above is mixed according to any proportion.
The stabilizer for chlorinated polyethylene applied to flame-retardant ABS production and the preparation method thereof comprise the following steps:
the method comprises the following steps: accurately weighing the raw materials according to a formula, adding talcum powder and hydrated sodium perchlorate into a stirrer, and stirring for 5min at 40 ℃ to obtain a mixture A;
step two: adding an antioxidant, hydrotalcite, 4A zeolite and dipentaerythritol into the mixture A obtained in the first step, and stirring for 5min at 40 ℃ to obtain a mixture B;
step three: and (2) adding 6-amino-1, 3-dimethyl uracil, dihydropyridine carboxylate and odorless phosphite into the mixture B obtained in the second step, stirring for 15min at 45 ℃, and cooling to obtain the stabilizer for the chlorinated polyethylene for producing the flame-retardant ABS.
Comparative example 1:
and (3) uniformly mixing 10 parts by weight of organic tin stabilizer, calcium zinc stabilizer and calcium stearate to obtain the contrast stabilizer.
Test example 1:
the stabilizer samples of examples 1-4 of the invention and 6g of the stabilizer of comparative example 1 were weighed separately, and 5 parts of 200g of chlorinated polyethylene were weighed separately and mixed with the stabilizer and then kneaded on an open mill at 135 + -2 ℃ for 3min to obtain a sheet. Then, the sample pieces were made into 10 strips of 40mm × 25mm, placed on an aluminum foil, and put into a 401A type aging test box at 190 + -1 deg.C, and one piece was taken out every 10 min. The yellowness values of the formulations were measured at different times according to ASTM D1925-70, the specific results are given in Table 1:
TABLE 1
Experimental data show that compared with a comparative example, the chlorinated polyethylene added with the stabilizing agent has better initial whiteness and corresponding long-term stability.
Test example 2
Weighing 3g of the stabilizer in examples 1-4 of the invention and 3g of the stabilizer in comparative example 1, weighing 5 parts of 100g of chlorinated polyethylene, respectively uniformly mixing, and testing the thermal stability of the chlorinated polyethylene mixture by a Congo red test paper method according to the specification of GB/T2917.1, wherein the testing temperature is 220 ℃, and the experimental results are shown in Table 2:
TABLE 2
Experimental data show that after the stabilizer is used for chlorinated polyethylene for producing flame-retardant ABS, the thermal stability time is obviously increased, and the improvement of the color difference stability and the long-term whiteness of the flame-retardant ABS product in the production process is greatly facilitated.
In conclusion, the invention provides a stabilizer for chlorinated polyethylene for producing flame-retardant ABS, which comprises the following components in parts by weight: 10-50 parts of 6-amino-1, 3-dimethyl uracil, 0-20 parts of dihydropyridine carboxylate, 0-10 parts of odorless phosphite ester, 0-10 parts of dipentaerythritol, 10-50 parts of 4A zeolite, 5-35 parts of hydrotalcite, 1-10 parts of hydrated sodium perchlorate, 5-10 parts of superfine talcum powder and 1-10 parts of antioxidant, the stabilizer has the following technical effects of absorbing hydrogen chloride by reacting with the hydrogen chloride, restraining further catalytic decomposition of CPE, improving the thermal stability of the CPE by using chlorinated polyethylene such as 6-amino-1, 3-dimethyl uracil, dihydropyridine carboxylate and odorless phosphite ester, and ensuring the initial whiteness and long-term stability for producing the flame-retardant ABS product.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it should be understood that various changes and modifications can be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in the indicated orientations and positional relationships and are used merely for convenience in describing the present invention and to simplify the description, but do not indicate or imply that the referenced devices or components must have a particular orientation, be constructed and operated in a particular orientation, and are therefore not to be considered limiting of the present invention. Furthermore, the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or to implicitly indicate a number of the indicated technical features. Thus, a feature defined as "first," "second," etc. may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
Claims (3)
1. The stabilizer for the chlorinated polyethylene for producing the flame-retardant ABS is characterized by comprising the following components in parts by weight: 10 to 50 parts of 6-amino-1, 3-dimethyl uracil, 0 to 20 parts of dihydropyridine carboxylate, 0 to 10 parts of odorless phosphite ester, 0 to 10 parts of dipentaerythritol, 10 to 50 parts of 4A zeolite, 5 to 35 parts of hydrotalcite, 1 to 10 parts of hydrated sodium perchlorate, 5 to 10 parts of superfine talcum powder and 1 to 10 parts of antioxidant.
2. The stabilizer for chlorinated polyethylene used in flame retardant ABS production as claimed in claim 1, wherein the antioxidant is one or a mixture of more than one of β - (3, 5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] pentaerythritol, tris [2, 4-di-tert-butylphenyl ] phosphite and 1,3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanuric acid in any ratio.
3. A preparation method for preparing the stabilizer for chlorinated polyethylene for flame retardant ABS production as claimed in any one of claims 1-2, wherein the preparation method comprises the following steps:
the method comprises the following steps: accurately weighing the raw materials according to the formula. Adding talcum powder and hydrated sodium perchlorate into a stirrer, and stirring for 5-8min at 30-40 ℃ to obtain a mixture A;
step two: adding an antioxidant, hydrotalcite, 4A zeolite and dipentaerythritol into the mixture A obtained in the first step, and stirring for 5-10min at the temperature of 30-50 ℃ to obtain a mixture B;
step three: and (2) adding 6-amino-1, 3-dimethyl uracil, dihydropyridine carboxylate and odorless phosphite into the mixture B obtained in the second step, stirring for 10-15min at the temperature of 30-50 ℃, and cooling to obtain the stabilizer for the chlorinated polyethylene for producing the flame-retardant ABS.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002006392A1 (en) * | 2000-07-14 | 2002-01-24 | Akzo Nobel N.V. | Stabilizer compositions comprsing a monomeric dihydropyridine derivative and their use |
| US20040204522A1 (en) * | 2003-04-11 | 2004-10-14 | Austen Steven Christopher | Thermal stabilizer compositions for halogen-containing vinyl polymers |
| CN105255048A (en) * | 2015-10-30 | 2016-01-20 | 永高股份有限公司 | Preparation method of high-performance environment-friendly U-PVC (unplasticized-polyvinyl chloride) pipe |
| CN107540618A (en) * | 2017-08-01 | 2018-01-05 | 新华制药（寿光）有限公司 | A kind of preparation method of the FU dimethyl of 6 amino 1,3 |
| CN109721886A (en) * | 2018-12-28 | 2019-05-07 | 山东三义实业股份有限公司 | PVC environment friendly transparent zinc-base heat stabilizer and its preparation process |
-
2022
- 2022-10-10 CN CN202211232959.9A patent/CN115594886B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002006392A1 (en) * | 2000-07-14 | 2002-01-24 | Akzo Nobel N.V. | Stabilizer compositions comprsing a monomeric dihydropyridine derivative and their use |
| US20040204522A1 (en) * | 2003-04-11 | 2004-10-14 | Austen Steven Christopher | Thermal stabilizer compositions for halogen-containing vinyl polymers |
| CN105255048A (en) * | 2015-10-30 | 2016-01-20 | 永高股份有限公司 | Preparation method of high-performance environment-friendly U-PVC (unplasticized-polyvinyl chloride) pipe |
| CN107540618A (en) * | 2017-08-01 | 2018-01-05 | 新华制药（寿光）有限公司 | A kind of preparation method of the FU dimethyl of 6 amino 1,3 |
| CN109721886A (en) * | 2018-12-28 | 2019-05-07 | 山东三义实业股份有限公司 | PVC environment friendly transparent zinc-base heat stabilizer and its preparation process |
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| CN115594886B (en) | 2023-06-23 |
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