CN110698599A - Efficient environment-friendly PVC lubricant and preparation method thereof - Google Patents
Efficient environment-friendly PVC lubricant and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F255/00—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00
- C08F255/02—Macromolecular compounds obtained by polymerising monomers on to polymers of hydrocarbons as defined in group C08F10/00 on to polymers of olefins having two or three carbon atoms
- C08F255/023—On to modified polymers, e.g. chlorinated polymers
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- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- 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
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- 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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- 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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Abstract
The invention relates to a preparation method of a PVC (polyvinyl chloride) auxiliary agent, in particular to a high-efficiency environment-friendly PVC lubricant and a preparation method thereof, belonging to the technical field of plastic products. An efficient environment-friendly PVC lubricant is mainly prepared by mixing the following components in parts by weight: and (2) component A: 5-50 parts of fatty acid, 5-95 parts of metal soap, 5-95 parts of carboxylic ester, 5-95 parts of fatty amide, 5-95 parts of fatty alcohol, 5-95 parts of hydrocarbon wax, 1-15 parts of epoxidized soybean oil, 1-15 parts of phosphite ester, 3-10 parts of polytetrafluoroethylene wax and 2-5 parts of coupling agent; and (B) component: the total weight of the component A is taken as 100 parts, and the component A comprises the following components: 0.3-0.5 part of peroxide crosslinking agent and 6-15 parts of maleic anhydride. The efficient environment-friendly PVC lubricant has the advantages of improving the compatibility of the lubricant and PVC and better lubricating effect, and meanwhile, the process is simple and is suitable for production and processing of PVC products with different stable systems.
Description
Technical Field
The invention relates to a preparation method of a PVC (polyvinyl chloride) auxiliary agent, in particular to a high-efficiency environment-friendly PVC lubricant and a preparation method thereof, belonging to the technical field of plastic products.
Background
Polyvinyl Chloride (PVC) is one of five general-purpose plastics in the world, has the characteristics of low price, good plasticity, flame retardancy, weather resistance, corrosion resistance, water resistance and chemical corrosion resistance, and better comprehensive mechanical property and electrical insulation property, is widely applied to light industry, agriculture, building materials, packaging, electric power and other departments, and plays a very important role in the field of plastics. Because the molecular chain of PVC contains unstable chlorine atoms, some defect structures are inevitably generated in the processing process, and the defect structures can cause that PVC is very easy to degrade. PVC polarity is stronger, and stronger interaction and frictional force exist between the molecular levels in the fusant and between the fusant and metal in the processing process, so the processing problems of high fusant viscosity, large material shearing friction heat generation, serious adhesion of the fusant to the metal surface of processing equipment and the like exist. These problems and the superposition of thermal instability lead to PVC which is very difficult to thermoplastically process. Therefore, in the formula, besides a stabilizing system, a filler system, a pigment system and a foaming system, the lubricating system has great influence on the processing performance, the appearance and various physical indexes of the product. Because of the small dosage, the important function is easy to ignore, and the processability of PVC and many defects of products are closely related to the selection and the proportion of the lubricant.
The Wu Mao Ying professor of Guangdong university of industry carries out research on the lubricating effect and mechanism of polyethylene wax and calcium stearate on PVC, reports a method for evaluating the lubricating effect of a lubricant on metal by using a torque rheometer to test the critical demolding dosage of lubrication, and has great guiding effect on the research and application of the lubricant by the established system test evaluation method; the influence of the lubricant on the PVC gel temperature and gel time is researched by Jiyubi and the like of Beijing chemical university; the Cannization group poplar waves reviewed the important role and common system of lubricants in PVC profiles.
Although PVC lubricants have been studied more by domestic institutions, most of them focus on academic research and relatively few research has been conducted on the type of application for industrial applications. A small amount of PVC lubricants reported in domestic patents are mostly liquid, have high requirements on production processes, are not beneficial to process simplification and production of fine chemical enterprises, and greatly reduce the mechanical properties of materials to be always subjected to industrial fouling. The existing process is mostly a mixture of one or two lubricants, has a narrow application range and cannot deal with the production process of PVC products with different stable systems; in addition, stearic acid or paraffin wax is singly used as a lubricant which is easy to volatilize and separate out in a large amount in the high-temperature high-vacuum processing process to cause loss; the use of a large amount of zinc stearate can cause PVC zinc burning, and the appearance of the product is seriously influenced; the amide lubricant has good effect, but the cost is too high, so that the use of the amide lubricant in the PVC field is limited; finally, electrostatic damage and dust pollution are also a great problem which troubles the PVC industry.
In order to meet the actual requirements of the current domestic fine chemical industry, the research and development of a composite granular efficient environment-friendly lubricant for PVC with a simple process is urgently needed, and the lubricant is suitable for the production and processing of PVC products with different stable systems.
Disclosure of Invention
The invention aims to provide an efficient environment-friendly PVC lubricant which has the advantages of good compatibility, high lubrication efficiency, rapid promotion of plasticization, improvement of filler addition amount, reduction of production cost, simple process and suitability for production and processing of PVC products with different stable systems.
The technical scheme adopted by the invention for solving the technical problems is as follows:
an efficient environment-friendly PVC lubricant is mainly prepared by mixing the following components in parts by weight: and (2) component A: 5-50 parts of fatty acid, 5-95 parts of metal soap, 5-95 parts of carboxylic ester, 5-95 parts of fatty amide, 5-95 parts of fatty alcohol, 5-95 parts of hydrocarbon wax, 1-15 parts of epoxidized soybean oil, 1-15 parts of phosphite ester, 3-10 parts of polytetrafluoroethylene wax and 2-5 parts of coupling agent; and (B) component: the total weight of the component A is taken as 100 parts, and the component A comprises the following components: 0.3-0.5 part of peroxide crosslinking agent and 6-15 parts of maleic anhydride.
The invention applies the concepts of complementation and offset effect of internal and external lubrication to the research and development of PVC lubricant, improves the lubrication effect, simultaneously ensures that PVC is not under-plasticized or over-plasticized in the processing process, and ensures the stability and continuity of the PVC extrusion production process; liquid lubricants (oleic acid, epoxidized soybean oil and glyceryl oleate) are introduced, so that dust pollution of workplaces is effectively inhibited, and potential dust explosion hidden dangers are eliminated; the metal soap is used as an auxiliary external lubricant, the synergistic effect of the metal soap and the external lubricant is fully exerted, and the thermal stability of PVC is improved while the lubricating effect is improved.
Preferably, the lubricant is prepared by mixing the following components in parts by weight: and (2) component A: 20-30 parts of fatty acid, 10-40 parts of metal soap, 20-60 parts of carboxylic ester, 5-30 parts of fatty amide, 5-10 parts of fatty alcohol, 20-60 parts of hydrocarbon wax, 1-15 parts of epoxidized soybean oil, 1-5 parts of phosphite ester, 3-10 parts of polytetrafluoroethylene wax and 2-5 parts of coupling agent; and (B) component: the total weight of the component A is taken as 100 parts, and the component A comprises the following components: 0.3-0.5 part of peroxide crosslinking agent and 6-15 parts of maleic anhydride.
Preferably, the fatty acid is selected from one or more of stearic acid (HSt), oleic acid, palmitic acid or myristic acid, preferably one or two of stearic acid and oleic acid;
the metal soap is zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, sodium stearate, zinc oleate, calcium oleate, sodium oleate or lithium stearate;
the carboxylic ester is one or more of glyceryl monostearate and glyceryl oleate, preferably glyceryl monostearate; the fatty amide is one or more of Ethylene Bis Stearamide (EBS), hydroxyethyl ethylene bis stearamide (modified EBS), ethylene bis oleamide, polar amide wax or stearic acid amide;
the fatty alcohol is one or more of stearyl alcohol, cetyl alcohol, polyethylene glycol or polyethylene glycol derivatives;
the hydrocarbon wax is one or more of paraffin, chlorinated paraffin, Fischer-Tropsch wax (FT wax), polyethylene wax (PE wax), oxidized polyethylene wax (OPE wax), polypropylene wax (PP wax), ethylene-vinyl acetate copolymer wax (EVA wax) or montmorillonite wax;
the phosphite ester is one or more of dioctyl pentaerythritol diphosphite, phenol-free phosphite or carbon-based-4, 4-diiso-methylene-fatty alcohol-phosphate chelating polymer.
Preferably, the lubricant is prepared by mixing the following components in parts by weight: 10-25 parts of stearic acid, 0-5 parts of oleic acid, 0-10 parts of sodium stearate, 0-8 parts of calcium stearate, 0-10 parts of lithium stearate, 5-10 parts of glyceryl oleate, 15-20 parts of glyceryl monostearate, 0-20 parts of hydroxyethyl ethylene bis stearamide, 0-20 parts of ethylene bis oleamide, 03-5 parts of polyethylene glycol PEG40003, 6A0-30 parts of PE wax, 629A10-20 parts of PE wax, 10-25 parts of OPE wax and 5-6 parts of carbon-based-4, 4-diisomethylene-fatty alcohol-phosphate ester chelate polymer.
The preparation method of the efficient environment-friendly PVC lubricant comprises the following steps: the components are proportioned according to a certain proportion and mixed uniformly by a mixer to obtain a composite powder PVC lubricant semi-finished product, then 100 parts of the mixed semi-finished product is added into an enamel reaction kettle, the temperature is raised to 140-160 ℃, and after the material is completely melted, 3-5m of the semi-finished product is introduced into each 100kg of the semi-finished product3The semi-finished product is subjected to high-temperature oxidation treatment by the air per min to improve the polarity and compatibility of the mixed components, and is subjected to heat preservation for 1-1.5 hours at the temperature of 140-; after the oxidation is finished, adding a peroxide crosslinking agent and maleic anhydride, continuously stirring and preserving the heat at the temperature of 150 ℃ and 170 ℃ for 0.5 to 1 hour to finish the grafting reaction of the mixed components; and (3) feeding the mixed components subjected to oxidation grafting into a granulation tower, allowing the materials to pass through a high-pressure nozzle and then settle from the top of the tower in a mist shape, and allowing the materials to contact with cold air rising from the bottom of the tower during the process and condensing into small beaded particles to obtain the finished PVC lubricant.
Compared with the prior art, the invention has the beneficial effects that:
1. the epoxidized soybean oil which is a lubricant with the function of a heat stabilizer is introduced, so that the application range of the lubricant in a lead salt stabilizing system, an organic tin stabilizing system and a calcium-zinc stabilizing system is widened, and meanwhile, the dosage of the stabilizer can be greatly reduced.
2. The fatty alcohol is introduced into the system and compounded with the fatty alcohol lubricant, so that the static problem in the processing process of the lubricant is solved, and the static damage in the processing and using processes of PVC is reduced.
3. The epoxidized soybean oil, the glyceryl oleate, the liquid phosphite ester and the like are introduced into the system, so that the dust pollution of the product is effectively inhibited, and the environment of a working place of a downstream manufacturer is improved.
4. The water-soluble fatty acid sodium salt is introduced into a PVC system for the first time, and the compatibility of the filler and the polymer is greatly improved by utilizing the strong basicity and the water solubility of the fatty acid sodium salt.
5. The EVA wax is introduced into a PVC system for the first time, has stronger synergistic effect with other lubricating components, and can obviously improve the external lubricating effect.
6. The lubricant packaged in one package is subjected to deep oxidation (air ventilation) for the first time, so that the lubricating components and the compatibility of the lubricating components and PVC are improved, and the synergistic effect among the components is greatly improved.
7. The mixed lubricant is subjected to maleic anhydride grafting treatment, so that the polarity of the lubricant and the compatibility with PVC are further improved, the compatibility between the polymer and the filler is better improved, and the friction between the filler and the polymer and between the filler and the screw rod is reduced.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the practice of the invention is not limited to the following examples, and that any variations and/or modifications may be made thereto without departing from the scope of the invention.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Examples 1 to 6
A preparation method of a high-efficiency environment-friendly PVC lubricant comprises the following steps:
the components shown in the table 1 are proportioned according to the proportion and evenly mixed by a mixer to obtain a composite powder PVC lubricant semi-finished product, then the mixed semi-finished product is added into an enamel reaction kettle, the temperature is increased to 140-3Min air to semi-finished productHigh-temperature oxidation treatment is carried out to improve the polarity and compatibility of the mixed components, and the temperature is kept for 1 to 1.5 hours at the temperature of 140 ℃ and 160 ℃ under the condition of air ventilation;
adding a peroxide crosslinking agent and maleic anhydride after the oxidation is finished, continuously stirring and preserving the heat at the temperature of 150 ℃ and 170 ℃ for 0.5 hour to finish the grafting reaction of the mixed components; wherein, 0.4kg of peroxide crosslinking agent and 10kg of maleic anhydride are added into each 100kg of semi-finished product;
and (3) feeding the mixed components subjected to oxidation grafting into a granulation tower, allowing the materials to pass through a high-pressure nozzle and then settle from the top of the tower in a mist shape, and allowing the materials to contact with cold air rising from the bottom of the tower during the process and condensing into small beaded particles to obtain the finished PVC lubricant.
TABLE 1 raw material proportions and Process conditions (unit: kg)
In order to verify the effect, the efficient and environment-friendly PVC lubricant prepared in each embodiment of the invention and the existing commercially available PVC composite lubricant (comparative example 1) are subjected to a production test of PVC products, and the differences of the two products are compared, which is specifically shown in Table 2.
Table 2 results of performance testing
The torque N.m and the discharging speed of the torque rheometer are process data of the PVC lubricant in production, and the data in the table 2 can show that the efficient environment-friendly PVC lubricant has the advantages of smoother surface, good whiteness and good ultraviolet color fastness when used for preparing PVC products.
The above-described embodiments are only preferred embodiments of the present invention, and are not intended to limit the present invention in any way, and other variations and modifications may be made without departing from the spirit of the invention as set forth in the claims.
Claims (5)
1. The efficient environment-friendly PVC lubricant is characterized by being prepared by mixing the following components in parts by weight:
and (2) component A: 5-50 parts of fatty acid, 5-95 parts of metal soap, 5-95 parts of carboxylic ester, 5-95 parts of fatty amide, 5-95 parts of fatty alcohol, 5-95 parts of hydrocarbon wax, 1-15 parts of epoxidized soybean oil, 1-15 parts of phosphite ester, 3-10 parts of polytetrafluoroethylene wax and 2-5 parts of coupling agent;
and (B) component: the total weight of the component A is taken as 100 parts, and the component A comprises the following components: 0.3-0.5 part of peroxide crosslinking agent and 6-15 parts of maleic anhydride.
2. The efficient and environment-friendly PVC lubricant as claimed in claim 1, characterized in that the lubricant is mainly prepared by mixing the following components in parts by weight:
and (2) component A: 20-30 parts of fatty acid, 10-40 parts of metal soap, 20-60 parts of carboxylic ester, 5-30 parts of fatty amide, 5-10 parts of fatty alcohol, 20-60 parts of hydrocarbon wax, 1-15 parts of epoxidized soybean oil, 1-5 parts of phosphite ester, 3-10 parts of polytetrafluoroethylene wax and 2-5 parts of coupling agent;
and (B) component: the total weight of the component A is taken as 100 parts, and the component A comprises the following components: 0.3-0.5 part of peroxide crosslinking agent and 6-15 parts of maleic anhydride.
3. The efficient, environmentally friendly PVC lubricant of claim 1, wherein: the fatty acid is selected from one or more of stearic acid (HSt), oleic acid, palmitic acid or myristic acid, preferably one or two of stearic acid and oleic acid;
the metal soap is zinc stearate, calcium stearate, magnesium stearate, aluminum stearate, sodium stearate, zinc oleate, calcium oleate, sodium oleate or lithium stearate;
the carboxylic ester is one or more of glyceryl monostearate and glyceryl oleate, preferably glyceryl monostearate;
the fatty amide is one or more of Ethylene Bis Stearamide (EBS), hydroxyethyl ethylene bis stearamide (modified EBS), ethylene bis oleamide, polar amide wax or stearic acid amide;
the fatty alcohol is one or more of stearyl alcohol, cetyl alcohol, polyethylene glycol or polyethylene glycol derivatives;
the hydrocarbon wax is one or more of paraffin, chlorinated paraffin, Fischer-Tropsch wax (FT wax), polyethylene wax (PE wax), oxidized polyethylene wax (OPE wax), polypropylene wax (PP wax), ethylene-vinyl acetate copolymer wax (EVA wax) or montmorillonite wax;
the phosphite ester is one or more of dioctyl pentaerythritol diphosphite, phenol-free phosphite or carbon-based-4, 4-diiso-methylene-fatty alcohol-phosphate chelating polymer.
4. The efficient and environment-friendly PVC lubricant as claimed in claim 1, characterized in that the lubricant is mainly prepared by mixing the following components in parts by weight:
10-25 parts of stearic acid,
0-5 parts of oleic acid,
0-10 parts of sodium stearate,
0-8 parts of calcium stearate,
0-10 parts of lithium stearate,
5-10 parts of glyceryl oleate,
15-20 parts of glycerin monostearate,
0-20 parts of hydroxyethyl ethylene bis stearamide,
0-20 parts of ethylene bis-oleamide,
Polyethylene glycol PEG40003-5 weight portions,
0-30 parts of PE wax AC6A0,
PE wax AC629A10 parts by weight and,
10-25 parts of OPE wax,
5-6 parts of a carbon-based-4, 4-diiso-methylene-fatty alcohol-phosphate chelating compound polymer.
5. A method for preparing the efficient and environment-friendly PVC lubricant according to claim 1, characterized in that the method comprises the steps of:
the components are proportioned according to a certain proportion and mixed uniformly by a mixer to obtain a composite powder PVC lubricant semi-finished product, then 100 parts of the mixed semi-finished product is added into an enamel reaction kettle, the temperature is raised to 140-Into 3-5m3The semi-finished product is subjected to high-temperature oxidation treatment by the air per min to improve the polarity and compatibility of the mixed components, and is subjected to heat preservation for 1-1.5 hours at the temperature of 140-; after the oxidation is finished, adding a peroxide crosslinking agent and maleic anhydride, continuously stirring and preserving the heat at the temperature of 150 ℃ and 170 ℃ for 0.5 to 1 hour to finish the grafting reaction of the mixed components; and (3) feeding the mixed components subjected to oxidation grafting into a granulation tower, allowing the materials to pass through a high-pressure nozzle and then settle from the top of the tower in a mist shape, and allowing the materials to contact with cold air rising from the bottom of the tower during the process and condensing into small beaded particles to obtain the finished PVC lubricant.
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| CN114805982A (en) * | 2022-04-18 | 2022-07-29 | 嘉应学院 | Luminescent material and preparation method thereof |
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| CN111607238A (en) * | 2020-07-03 | 2020-09-01 | 江苏法迩蜡业有限公司 | Composite wax for PVC (polyvinyl chloride) stone-plastic floor and preparation method thereof |
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| CN114805982A (en) * | 2022-04-18 | 2022-07-29 | 嘉应学院 | Luminescent material and preparation method thereof |
| CN114805982B (en) * | 2022-04-18 | 2023-08-18 | 嘉应学院 | Luminescent material and preparation method thereof |
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