CN113683851B - Method for improving processability of chlorinated polyvinyl chloride resin - Google Patents
Method for improving processability of chlorinated polyvinyl chloride resin Download PDFInfo
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- CN113683851B CN113683851B CN202111082220.XA CN202111082220A CN113683851B CN 113683851 B CN113683851 B CN 113683851B CN 202111082220 A CN202111082220 A CN 202111082220A CN 113683851 B CN113683851 B CN 113683851B
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- 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
- C08L27/22—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 modified by chemical after-treatment
- C08L27/24—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 modified by chemical after-treatment halogenated
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Abstract
The invention discloses a method for improving the processability of chlorinated polyvinyl chloride resin, which is characterized in that in the processing process of the chlorinated polyvinyl chloride resin, chlorinated polyethylene with ultrahigh molecular weight is added; the viscosity average molecular weight of the chlorinated polyethylene with ultrahigh molecular weight is more than 100 ten thousand, and the chlorine content is 20-40wt%. According to the invention, the chlorinated polyethylene with ultrahigh molecular weight is used as a processing modifier of the chlorinated polyvinyl chloride resin, so that the obtained mixed material has good demolding performance, the toughness of the mixed material is improved, and the Vicat softening point is not influenced.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a method for improving the processability of chlorinated polyvinyl chloride resin.
Background
Chlorinated polyvinyl chloride (CPVC) resin is prepared by introducing chlorine atoms into a molecular structure of PVC resin through chlorination reaction, so that the chlorine content is increased from 56% of common PVC resin to 61% -75%. The content of chlorine is increased, various performances of the PVC resin are improved, the PVC resin has good chemical corrosion resistance, flame retardance and insulativity, the heat resistance is greatly superior to that of the PVC resin, and the CPVC resin can be applied to the fields of chemical industry, building materials, metallurgy, shipbuilding, electrical appliances and adhesives.
The CPVC resin has poor processability due to high chlorine content. Compared with general PVC resin, the PVC resin has much higher processing difficulty, and particularly in the processing process, chlorinated polyvinyl chloride has stronger polarity, so that the chlorinated polyvinyl chloride has higher tendency of adhering to processing equipment than general polar compounds, thereby easily causing a series of phenomena such as decomposition, air bubbles and the like in the production process due to easy material adhesion in the processing process, and the PVC resin has very high processing temperature and is not easy to plasticize under the condition of not adding a processing aid.
The addition of certain amounts of internal and external lubricants can improve the adhesion properties of the CPVC resin and metal mold and lower the plasticizing temperature, but most lubricants, especially those compatible with CPVC, have a lower melting point, and thus the vicat softening point is lowered very much, which affects the use of CPVC articles. The external lubricant is unstable and easily precipitates during processing, so that CPVC products with smooth surfaces and good processability cannot be obtained.
The addition of processing aids can also serve to improve adhesion of the CPVC resin to the metal mold and lower the plasticizing temperature of the CPVC. For example, CN02110265.1 discloses a processing aid for improving the processability of CPVC without affecting the Vicat softening point, and the main component of the processing aid is acrylonitrile-methylstyrene-styrene copolymer. CN200910198834.7 discloses a method for improving CPVC processability by adding thermoplastic polyurethane, which effectively enhances the tensile strength of CPVC compounds, and also increases their elongation and impact strength, and improves the adhesion properties of CPVC resins and metals.
In general, how to improve CPVC processability is still one of the technical issues that need to be continuously studied to promote CPVC articles.
Disclosure of Invention
The invention aims to provide a method for improving the processability of chlorinated polyvinyl chloride resin, which can obviously improve the plasticizing performance in the processing process of CPVC resin, reduce the adhesion between the CPVC resin and a metal mould, improve the toughness of the CPVC resin and have no influence on the Vicat softening point.
The method for improving the processability of the CPVC resin is to add ultrahigh molecular weight chlorinated polyethylene in the CPVC resin processing process. The polymerization degree of the CPVC resin is 600-1100, and the chlorine content is 65-70%. The viscosity average molecular weight of the chlorinated polyethylene with ultrahigh molecular weight is more than 100 ten thousand, and the chlorine content is 20-40wt%. The amount of the ultra-high molecular weight chlorinated polyethylene added is 1 to 10 parts, preferably 1 to 3 parts, based on 100 parts by weight of the CPVC resin.
Other conventional adjuvants may also be added during the processing of the CPVC resin. Other additives include heat stabilizers, internal lubricants, external lubricants, impact modifiers, processing aids, inorganic fillers, and other additives used in the processing of the CPVC resin.
The heat stabilizer is one or more of a tin stabilizer, a lead stabilizer, a calcium-zinc stabilizer and a rare earth stabilizer, and the addition amount is 3-5 parts.
The internal lubricant is one or more of glycerol monostearate, butyl stearate, dibutyl phthalate, dioctyl phthalate, epoxidized soybean oil and lauryl alcohol, and the addition amount is 0.5-3 parts.
The external lubricant is one or more of high-temperature paraffin and oxidized polyethylene wax, and the addition amount is 0.5-3 parts.
The impact modifier is one or more of CPE135A, MBS and ACR50, and the adding amount is 3-15 parts.
The processing aid is one or more of ACR401 and ACR801, and the addition amount is 1-10 parts.
The inorganic filler is one or more of calcium carbonate, titanium dioxide and talcum powder, and the addition amount is 1-30 parts.
The method for improving the processability of the CPVC resin comprises the following steps:
adding the CPVC resin, the chlorinated polyethylene with ultrahigh molecular weight and the heat stabilizer into a high-speed mixer for mixing, heating to 60-100 ℃, adding the internal lubricant, the external lubricant, the impact modifier, the processing aid and the inorganic filler, and continuously mixing to heat to 100-120 ℃. And then putting the mixture into a low-speed mixer, introducing cold water for quick cooling, cooling to below 60 ℃, and discharging to obtain a chlorinated polyvinyl chloride resin finished product with good processability.
The invention has the beneficial effects that: the chlorinated polyethylene with ultrahigh molecular weight is used as an organic rigid particle, combines the advantages of the chlorinated polyethylene with ultrahigh molecular weight, not only has better rigidity, but also has good compatibility with CPVC resin. The addition of the chlorinated polyethylene with ultrahigh molecular weight reduces the viscosity of the CPVC mixture at high temperature, improves the adhesion phenomenon of the CPVC mixture and a metal mold, improves the processing fluidity, improves the toughness of the CPVC mixture, and does not influence the Vicat softening point.
Detailed Description
In order that those skilled in the art will better understand the manner in which the present invention is made, a more complete description of the method of improving the processability of chlorinated polyvinyl chloride resin of the present invention will now be provided in connection with the detailed description.
The test mode is as follows:
dynamic thermal stability test: and (3) measuring by using a Haake rheometer, setting the temperature of a mixer to be 180 ℃, setting the rotating speed of a rotor to be 30 revolutions per minute, weighing 71 grams of mixture, adding the mixture into the mixer, starting the rheometer, and finishing after the torque is constant for 5 minutes. The Vicat softening point is tested according to GB/T1633-2000, and the impact strength of the notch of the simply supported beam is tested according to GB/T1043.1-2008.
Example 1
100 parts of CPVC resin (polymerization degree is 1000, chlorine content is 67 percent), 3 parts of tin heat stabilizer and 3 parts of chlorinated polyethylene with ultrahigh molecular weight (viscosity average molecular weight is 120 ten thousand, chlorine content is 25 percent) are added into a high-speed mixer to be mixed, the temperature is increased to 60 ℃, 1 part of epoxidized soybean oil, 1 part of butyl stearate, 0.7 part of oxidized polyethylene wax, 135A 8 parts of CPE, 401 parts of ACR and 5 parts of calcium carbonate are added, and the mixture is continuously mixed to increase the temperature to 105 ℃. Then putting the mixture into a low-speed mixer, introducing cold water for quick cooling, cooling to below 60 ℃ and discharging.
Example 2
100 parts of CPVC resin (with the polymerization degree of 1000 and the chlorine content of 67 percent), 3 parts of tin heat stabilizer and 3 parts of chlorinated polyethylene with ultrahigh molecular weight (with the viscosity average molecular weight of 120 ten thousand and the chlorine content of 25 percent) are added into a high-speed mixer to be mixed, the temperature is raised to 60 ℃, 1 part of epoxidized soybean oil, 1 part of butyl stearate, 0.7 part of oxidized polyethylene wax, 8 parts of MBS, 401 parts of ACR and 5 parts of calcium carbonate are added, and the mixture is continuously mixed until the temperature is raised to 105 ℃. Then putting the mixture into a low-speed mixer, introducing cold water for quick cooling, cooling to below 60 ℃ and discharging.
Example 3
100 parts of CPVC resin (polymerization degree is 1000, chlorine content is 67%), 3 parts of tin heat stabilizer and 5 parts of chlorinated polyethylene with ultrahigh molecular weight (viscosity average molecular weight is 120 ten thousand, chlorine content is 25%) are added into a high-speed mixer to be mixed, the temperature is increased to 60 ℃, 1 part of epoxidized soybean oil, 1 part of butyl stearate, 0.7 part of oxidized polyethylene wax, 135A 8 parts of CPE, 401 parts of ACR and 5 parts of calcium carbonate are added, and the mixture is continuously mixed to increase the temperature to 105 ℃. Then putting the mixture into a low-speed mixer, introducing cold water for quick cooling, cooling to below 60 ℃ and discharging.
Example 4
100 parts of CPVC resin (polymerization degree is 1000, chlorine content is 67 percent), 3 parts of tin heat stabilizer and 3 parts of chlorinated polyethylene with ultrahigh molecular weight (viscosity average molecular weight is 120 ten thousand, chlorine content is 25 percent) are added into a high-speed mixer to be mixed, the temperature is increased to 60 ℃, 1 part of epoxidized soybean oil, 1 part of butyl stearate, 0.7 part of oxidized polyethylene wax, 135A 8 parts of CPE, 401 parts of ACR and 5 parts of titanium dioxide are added, and the mixture is continuously mixed to increase the temperature to 105 ℃. Then putting the mixture into a low-speed mixer, introducing cold water for quick cooling, cooling to below 60 ℃ and discharging.
Example 5
100 parts of CPVC resin (polymerization degree is 1000, chlorine content is 67%), 3 parts of calcium-zinc heat stabilizer and 3 parts of ultra-high molecular weight chlorinated polyethylene (viscosity average molecular weight is 120 ten thousand, chlorine content is 25%) are added into a high-speed mixer to be mixed, the temperature is increased to 60 ℃, 1 part of epoxidized soybean oil, 1 part of butyl stearate, 0.7 part of oxidized polyethylene wax, 135A 8 parts of CPE, 401 6 parts of ACR and 5 parts of calcium carbonate are added, and the mixture is continuously mixed to increase the temperature to 105 ℃. Then putting the mixture into a low-speed mixer, introducing cold water for quick cooling, cooling to below 60 ℃ and discharging.
Example 6
100 parts of CPVC resin (polymerization degree 670, chlorine content 70%), 3 parts of tin heat stabilizer and 3 parts of ultra-high molecular weight chlorinated polyethylene (viscosity average molecular weight 200 ten thousand, chlorine content 30%) are added into a high-speed mixer for mixing, the temperature is raised to 70 ℃, 1 part of epoxidized soybean oil, 1 part of butyl stearate, 0.7 part of oxidized polyethylene wax, 8 parts of CPE135A, 401 parts of ACR and 5 parts of calcium carbonate are added, and the mixture is continuously mixed until the temperature is raised to 105 ℃. Then putting the mixture into a low-speed mixer, introducing cold water for quick cooling, cooling to below 60 ℃ and discharging.
Comparative example 1
100 parts of CPVC resin (with chlorine content of 67 percent) and 3 parts of tin heat stabilizer are added into a high-speed mixer, the mixture is mixed, the temperature is raised to 60 ℃, 1 part of epoxidized soybean oil, 1 part of butyl stearate, 0.7 part of oxidized polyethylene wax, 135A 8 parts of CPE, 401 parts of ACR and 5 parts of calcium carbonate are added, and the mixture is continuously mixed to raise the temperature to 105 ℃. Then putting the mixture into a low-speed mixer, introducing cold water for quick cooling, cooling to below 60 ℃ and discharging.
Comparative example 2
Adding 100 parts of CPVC resin (with the chlorine content of 67%) and 3 parts of tin heat stabilizer into a high-speed mixer, mixing, heating to 60 ℃, adding 1 part of epoxidized soybean oil, 1 part of butyl stearate, 0.7 part of oxidized polyethylene wax, 135A 8 parts of CPE, 401 parts of ACR and 5 parts of calcium carbonate, and continuously mixing until the temperature is raised to 105 ℃. Then putting the mixture into a low-speed mixer, introducing cold water for quick cooling, cooling to below 60 ℃ and discharging.
As can be seen from Table 1, compared with the CPVC mixture without adding the ultrahigh molecular weight chlorinated polyethylene, the CPVC mixture adopting the technical scheme of the invention has the advantages that the impact strength of the notch of the simply supported beam is improved, the Vicat softening point can be effectively maintained, the adhesion performance with a metal mold is greatly improved, and the demolding performance is good.
Claims (6)
1. A method for improving the processability of chlorinated polyvinyl chloride resin is characterized in that in the processing process of the chlorinated polyvinyl chloride resin, chlorinated polyethylene with ultrahigh molecular weight is added; the viscosity average molecular weight of the chlorinated polyethylene with ultrahigh molecular weight is more than 100 ten thousand, and the chlorine content is 20-40wt%; the weight of the chlorinated polyethylene with ultrahigh molecular weight is 1 to 10 parts based on 100 parts by weight of the chlorinated polyvinyl chloride resin.
2. The method for improving the processability of a chlorinated polyvinyl chloride resin according to claim 1, wherein the degree of polymerization of the chlorinated polyvinyl chloride resin is 600 to 1100 and the chlorine content is 65 to 70%.
3. The method for improving the processability of a chlorinated polyvinyl chloride resin according to claim 1, wherein the ultra-high molecular weight chlorinated polyethylene is added in an amount of 1 to 3 parts by weight based on 100 parts by weight of the chlorinated polyvinyl chloride resin.
4. The method for improving the processability of chlorinated polyvinyl chloride resin according to claim 1, wherein other additives are further added during the processing of the chlorinated polyvinyl chloride resin.
5. The method for improving processability of a chlorinated polyvinyl chloride resin according to claim 4, wherein in the processing of the chlorinated polyvinyl chloride resin, based on 100 parts by weight of the chlorinated polyvinyl chloride resin, further added are:
3-5 parts of heat stabilizer
0.5 to 3 portions of internal lubricant
0.5 to 3 portions of external lubricant
3-15 parts of impact modifier
1-10 parts of processing aid
1-30 parts of inorganic filler
The heat stabilizer is one or more of a tin stabilizer, a lead stabilizer, a calcium-zinc stabilizer and a rare earth stabilizer;
the internal lubricant is one or more of glycerol monostearate, butyl stearate, dibutyl phthalate, dioctyl phthalate, epoxidized soybean oil and lauryl alcohol;
the external lubricant is one or more of high-temperature paraffin and oxidized polyethylene wax;
the impact modifier is one or more of CPE135A, MBS and ACR 50;
the inorganic filler is one or more of calcium carbonate, titanium dioxide and talcum powder.
6. The method for improving the processability of chlorinated polyvinyl chloride resin according to claim 1, comprising the steps of: adding CPVC resin, ultrahigh molecular weight chlorinated polyethylene and a heat stabilizer into a high-speed mixer for mixing, heating to 60-100 ℃, adding an internal lubricant, an external lubricant, an impact modifier, a processing aid and an inorganic filler, continuously mixing to heat to 100-120 ℃, then putting into a low-speed mixer, introducing cold water for quick cooling, cooling to below 60 ℃, and discharging to obtain a chlorinated polyvinyl chloride resin finished product with good processability.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5981663A (en) * | 1996-05-24 | 1999-11-09 | The B.F. Goodrich Company | Chlorinated polyvinyl chloride compound having excellent physical, chemical resistance and processing properties |
| CN101704978A (en) * | 2009-11-17 | 2010-05-12 | 上海氯碱化工股份有限公司 | Method for improving processability of chlorinated polyvinyl chloride resin |
| CN103265780A (en) * | 2013-05-07 | 2013-08-28 | 上海氯碱化工股份有限公司 | Chlorinated polyvinylchloride mixing material |
| CN105273343A (en) * | 2014-06-16 | 2016-01-27 | 上海氯碱化工股份有限公司 | Chlorinated polyvinyl chloride mixture |
| CN106543609A (en) * | 2016-10-12 | 2017-03-29 | 上海氯碱化工股份有限公司 | The method for improving chliorinated polyvinyl chloride processing characteristics |
| CN107266614A (en) * | 2017-08-08 | 2017-10-20 | 杭州新元化工技术开发有限公司 | A kind of super high molecular weight haloflex and preparation method thereof, device and application |
| CN110283412A (en) * | 2019-06-25 | 2019-09-27 | 潍坊亚星化学股份有限公司 | A kind of blended modified chlorinated pvc material and preparation method thereof |
-
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- 2021-09-15 CN CN202111082220.XA patent/CN113683851B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5981663A (en) * | 1996-05-24 | 1999-11-09 | The B.F. Goodrich Company | Chlorinated polyvinyl chloride compound having excellent physical, chemical resistance and processing properties |
| CN101704978A (en) * | 2009-11-17 | 2010-05-12 | 上海氯碱化工股份有限公司 | Method for improving processability of chlorinated polyvinyl chloride resin |
| CN103265780A (en) * | 2013-05-07 | 2013-08-28 | 上海氯碱化工股份有限公司 | Chlorinated polyvinylchloride mixing material |
| CN105273343A (en) * | 2014-06-16 | 2016-01-27 | 上海氯碱化工股份有限公司 | Chlorinated polyvinyl chloride mixture |
| CN106543609A (en) * | 2016-10-12 | 2017-03-29 | 上海氯碱化工股份有限公司 | The method for improving chliorinated polyvinyl chloride processing characteristics |
| CN107266614A (en) * | 2017-08-08 | 2017-10-20 | 杭州新元化工技术开发有限公司 | A kind of super high molecular weight haloflex and preparation method thereof, device and application |
| CN110283412A (en) * | 2019-06-25 | 2019-09-27 | 潍坊亚星化学股份有限公司 | A kind of blended modified chlorinated pvc material and preparation method thereof |
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