CN111303551A - Vinyl chloride resin compound and preparation method thereof - Google Patents
Vinyl chloride resin compound and preparation method thereof Download PDFInfo
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- CN111303551A CN111303551A CN201811517562.8A CN201811517562A CN111303551A CN 111303551 A CN111303551 A CN 111303551A CN 201811517562 A CN201811517562 A CN 201811517562A CN 111303551 A CN111303551 A CN 111303551A
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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
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
- C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
- C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride
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Abstract
The invention belongs to the field of high polymer materials, and discloses a vinyl chloride resin compound and a preparation method thereof. The preparation method of the vinyl chloride resin composite comprises the following steps: vinyl chloride resins in solid form are polymerized heterogeneously with isobutene or with a mixture of isobutene and other comonomers in the presence of a coinitiator and an electron donor. The vinyl chloride resin compound can be prepared in situ by adopting the method provided by the invention, wherein two phases of the chain segments of the vinyl chloride resin and the isobutylene polymer are uniformly dispersed, so that a novel vinyl chloride resin-based composite material with excellent comprehensive performance, which integrates improved mechanical property, plasticizing property, thermal stability and airtightness, is obtained, the production process is simple, and the production cost is saved.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a vinyl chloride resin compound and a preparation method thereof.
Background
Vinyl chloride resin is a generic name for polymers obtained by polymerizing vinyl chloride to obtain polyvinyl chloride or copolymerizing vinyl chloride with one or more other unsaturated compounds. Polyvinyl chloride (PVC) is one of five general resins in the world at present, has excellent overall performance-price ratio and outstanding advantages of flame retardancy, good transparency, chemical corrosion resistance, wear resistance and the like, is widely applied to multiple fields of pipelines, window frames, floors, wallpaper, curtains, cables, electric wires, coatings, packaging materials, medical tubes, blood bags, imitation leather and the like, but has insufficient thermal stability, toughness, impact strength and processability, and restricts the development and application of the PVC in fields with higher performance requirements (see: Chimingsheng, Zhang Henxi, research progress and prospect of polyvinyl chloride modification, and chlor-alkali in China, 2017 (05): 11-14). Chlorinated polyvinyl chloride is a product of further chlorination of polyvinyl chloride, and is a modified product of polyvinyl chloride.
Taking PVC as an example, the PVC has high melting temperature and high melt viscosity, and is difficult to process and mold by injection molding and extrusion, and the plasticizing and modifying effect can be achieved by adding a plasticizer into the PVC, wherein phthalate is the most widely used PVC plasticizer, but the migration of small molecular plasticizers causes harm to the environment and human health, and the application of phthalate plasticizers in the fields of clothing packaging, medical supplies, toys for children and the like is limited in European and American countries at present. Introduction of bulky steric hindrance or functional side groups on the molecular chain by graft modification, such as bonding of diisooctyl Phthalate on the PVC main chain, can effectively eliminate the problem of migration of the plasticizer, and the internal plasticization effect is good (see: Navarro R, Perrino M P, Tardajosm G, Reinecke H, Phthalate Plasticizers such as plasticizer coordinated to PVC: plastics with preserved plasticizer migration, Macromolecules,2010,43: 2377-. The vinyl chloride monomer and a second monomer (such as vinyl acetate, ethyl acrylate and the like) are copolymerized, so that the glass transition temperature of the PVC-based material can be reduced, and the plasticizing effect is achieved, but the mechanical property of the internally plasticized PVC material obtained by the method is greatly reduced, and the use requirement cannot be met. The introduction of bulky steric groups into the pendant groups of PVC can also achieve internal Plasticization, such as Grafting Hyperbranched Polyglycerol ester (HPG) onto the main chain of PVC, which can greatly reduce intermolecular forces, but has obvious Plasticization effect, but the synthesis process is complicated, and the thermal stability of PVC can be further damaged due to the low thermal decomposition temperature of the branched HPG (see: Kyu Won Lee, Jae Wo Chung, Seung-Yeop KWak, structural Enhanced Self-plasticity of Poly (vinyl chloride) via gradient coating of superabsorbent Polyglycerol, Macromol. Rapid Commun, 2016,37: 2045-.
Rigid PVC has poor toughness (especially low-temperature toughness), and is blended and compounded with elastomer toughening agents (such as nitrile rubber, chlorinated polyethylene, acrylonitrile-butadiene-styrene copolymer, etc.) or rigid particles (such as polymethyl methacrylate, polystyrene, nano silica, nano calcium carbonate, etc.) by physical methods, so that the toughness of PVC can be improved (see: Shokri AA, Bakhshandeh G R, Farahani T. D.An. innovative and hydraulic properties of NBR/PVC blends: influence of inorganic Polymer additives, mixing procedure and NBR form. Iranian Polymer Journal,2006,15(15): 227; Zhou Li, Wang Xin, Yu Sheng, Yang, Wu's ABS, PVC/ABS and PVC/blend system, and the structural and chemical properties of Qingdao system (university of Qingdao science and technology), 2003, (01): 48-52). However, the incompatibility of the system can cause the uneven distribution of the toughening agent and seriously affect the performance of the material, so that the toughening agent needs to be subjected to certain surface treatment before blending modification, and the process is more complicated (see: Chengshaohui, Songyinghu, Dupelhua, Chunrong, Zhengqiang, PVC/CPE/CaCO3Mechanical properties of the composite material, journal of materials science and engineering, 2011, 29 (06): 829-832, 845).
Polyisobutylene (PIB) is a polymer prepared by polymerizing isobutylene through positive (positive) ions, and has the characteristics of excellent air tightness, water tightness, aging resistance, electric insulation, heat resistance, cold resistance, dielectric property and the like. Isobutylene can be copolymerized with cationically polymerizable monomers (e.g., conjugated dienes or vinyl aromatics), such as isobutylene with a small amount of isoprene to produce butyl rubber, and isobutylene with a small amount of p-methylstyrene to produce isobutylene-based specialty elastomers. Although the defects of the PVC material can be improved to a certain extent by physically blending the PIB and the PVC, the toughness and the mechanical damping performance of the PVC material are improved, but the blending compatibility of the PIB and the PVC material is poor, the mixture is difficult to uniformly mix, and when the amount of the PIB exceeds 20 wt%, the performance of the blend is greatly reduced (see: Fanshixia, Zhang Fengyu, Yanhusei, Zhang Qingyu, the damping property of a polyvinyl chloride-low molecular weight polyisobutylene blend, applied chemistry, 1990, 7 (3): 51-53).
In the prior art, if PVC is used to initiate isobutylene cationic polymerization, there are problems of very low grafting efficiency and low grafting amount, and the preparation process usually requires a large amount of Lewis acid as a co-initiator and the introduction of expensive proton scavenger such as 2, 6-di-tert-butylpyridine (DtBP, about 400 yuan/g) into the polymerization system, and the post-treatment process is not easy to remove, which increases the process difficulty and the production cost (see: Kennedy J P, Graft Modification of Poly (viny1Chloride) and Related Reactions, Journal of Applied Polymer Science, 1972, 10: 2507-; pi Z, Kennedy J P, Cationic grading of Olefins from PVC the Effect of Reaction Conditions, Journal of Applied Polymer Science 2001,39: 1675-.
In conclusion, the PVC material has the problems of poor thermal stability, poor toughness, low impact strength and poor processability, and the traditional physical blending method can be used for modification, but has the problems of poor compatibility, small molecule migration, unstable material performance and the like; although the thermal stability, plasticity or toughness and the like can be improved by a chemical method, other properties are sacrificed, and the problems of high preparation cost, complex process, limitation and the like exist.
Disclosure of Invention
The object of the present invention is to overcome the above drawbacks of the prior art and to provide a novel vinyl chloride resin composite and a method for preparing the same.
Specifically, the invention provides a vinyl chloride resin compound, wherein the vinyl chloride resin compound comprises solid vinyl chloride resin solid and a vinyl chloride resin graft copolymer coated on the surface of the vinyl chloride resin solid, the vinyl chloride resin is selected from at least one of polyvinyl chloride, chlorinated polyvinyl chloride and a vinyl chloride-vinyl acetate copolymer, the vinyl chloride resin graft copolymer is a polymer which takes the polyvinyl chloride, the chlorinated polyvinyl chloride or the vinyl chloride-vinyl acetate copolymer as a main chain and is connected with a plurality of isobutylene-based polymer chain segment branches, and the total mass content of the isobutylene-based polymer chain segment branches is 5-50 wt% based on the total mass of the vinyl chloride resin compound.
The present invention also provides a method for preparing a vinyl chloride resin composite, the method comprising: vinyl chloride resins in solid form are polymerized heterogeneously with isobutene or with a mixture of isobutene and other comonomers in the presence of a coinitiator and an electron donor.
The present invention also provides a vinyl chloride resin composite prepared by the above method.
The method provided by the invention can be used for preparing the vinyl chloride resin compound in situ, wherein the vinyl chloride resin and the isobutylene polymer chain segment are uniformly dispersed, so that the novel vinyl chloride resin compound with excellent comprehensive performance, which integrates improved mechanical property, plasticizing property, thermal stability and airtightness, is obtained, the production process is simple, and the production cost is saved. The vinyl chloride resin compound has excellent mechanical properties, the tensile strength can reach 46MPa, the elongation at break can reach 45%, and compared with the corresponding vinyl chloride resin, the vinyl chloride resin compound achieves the effects of strengthening and toughening; the vinyl chloride resin compound has better processing performance and improved thermal stability, the decomposition temperature of the vinyl chloride resin compound is increased by up to 44 ℃ compared with the decomposition temperature of the corresponding vinyl chloride resin, and the processing window is widened; the vinyl chloride resin composite also has excellent gas barrier properties, which are improved by up to 20 times compared to corresponding vinyl chloride resins.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings.
FIG. 1 shows a schematic comparison of the tensile strength of the PVC/PVC-g-PIB composite prepared in example 2 according to the invention with that of comparative example 1.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
The vinyl chloride resin compound provided by the invention comprises solid vinyl chloride resin and a vinyl chloride resin graft copolymer coated on the surface of the vinyl chloride resin, wherein the vinyl chloride resin is selected from at least one of polyvinyl chloride, chlorinated polyvinyl chloride and a vinyl chloride-vinyl acetate copolymer, the vinyl chloride resin graft copolymer is a polymer which takes polyvinyl chloride, chlorinated polyvinyl chloride or a vinyl chloride-vinyl acetate copolymer as a main chain and is connected with a plurality of isobutylene-based polymer chain segment branches, and the total mass content of the isobutylene-based polymer chain segment branches is 5-50 wt%, preferably 7-45 wt%, and more preferably 9-40% based on the total mass of the vinyl chloride resin compound.
The isobutylene-based polymer segment branches can be isobutylene homopolymer segments and can also be copolymer segments of isobutylene and other comonomers, wherein when the isobutylene-based polymer segment branches are copolymer segments of isobutylene and other comonomers, the molar content of isobutylene structural units can be 95.0-99.9 mol%, the other comonomers are preferably conjugated dienes and/or vinyl aromatic hydrocarbons, specific examples of the conjugated dienes include but are not limited to at least one of 1, 3-butadiene, 1, 3-pentadiene and isoprene, specific examples of the vinyl aromatic hydrocarbons include but are not limited to at least one of styrene, p-methylstyrene, α -methylstyrene, p-methoxystyrene, p-chloromethylstyrene, p-tert-butylstyrene and p-tert-butylstyrene.
Polymer weight average molecular weight (M) of the vinyl chloride resinw) Preferably from 50 to 400kg/mol, more preferably from 60 to 380kg/mol, most preferably from 70 to 350 kg/mol; molecular weight distribution index Mw/MnPreferably 1.3-4.0, more preferably 1.4-3.5, most preferably 1.5-3.2.
The vinyl chloride resin is a product of suspension polymerization, emulsion polymerization or bulk polymerization of vinyl chloride, and is preferably in the form of particles or powder, and the particle diameter thereof is preferably 0.1 μm or more, more preferably 0.2 to 500 μm, further preferably 2 to 400 μm, and most preferably 5 to 370 μm. The vinyl chloride resin particles or powder may have a wide particle size distribution, and may be of a dense structure type or a loose structure type. The vinyl chloride resin has small particle size or loose structure and large specific surface area, and is beneficial to grafting more isobutylene-based polymer chain segments.
The preparation method of the vinyl chloride resin compound provided by the invention comprises the following steps: vinyl chloride resins in solid form are polymerized heterogeneously with isobutene or with a mixture of isobutene and other comonomers in the presence of a coinitiator and an electron donor. The term "heterogeneous polymerization" refers to a polymerization reaction carried out in a heterogeneous system.
The order of addition of the raw materials before the heterogeneous polymerization reaction is not particularly limited in the present invention. According to a preferred embodiment of the present invention, the method of heterogeneous polymerization comprises:
A. mixing solid vinyl chloride resin with isobutene and other comonomers optionally contained to form a heterogeneous system, wherein the heterogeneous system contains or does not contain a reaction medium, the reaction medium is an organic solvent or an aqueous phase medium or contains both an organic solvent and an aqueous phase medium, and the organic solvent is an inert liquid organic matter which does not dissolve the solid vinyl chloride resin but can disperse or swell the solid vinyl chloride resin;
B. and B, mixing the reaction system formed in the step A with a coinitiator and an electron donor to initiate heterogeneous polymerization.
According to the invention, the molar ratio of polyvinyl chloride, coinitiator, electron donor and isobutene may be (1.2X 10)-3-6.0×10-3)：(5.0×10-3-8.0×10-2)：(6.0×10-4-8.0×10-2): 1, preferably (1.4X 10)-3-5.5×10-3)：(5.5×10-3-7.5×10-2)：(6.5×10-4-7.0×10-2): 1, more preferably (1.8X 10)-3-5.0×10-3)：(6.0×10-3-7.0×10-2)：(7.0×10-4-6.0×10-2): 1. in addition, when other comonomers are present, the monomeric isobutylene may be present in a molar amount of 95.0 to 99.9 mol%.
As described above, the reaction medium in the heterogeneous solution may be an organic solvent, an aqueous medium, or both an organic solvent and an aqueous medium. Wherein the organic solvent can be selected from nonpolar organic solvents (such as pentane, hexane, heptane, octane, methylcyclohexane, etc.), low carbon number halogenated hydrocarbons (such as methyl chloride, dichloromethane), or a mixed solvent of two or more of them. The aqueous medium may be water and/or an aqueous reaction medium, wherein the water-soluble compound in the aqueous reaction medium is selected from one or more of alkali metal salts IAP or ammonium salts, inorganic protonic acids, organic acid plasma compounds or alcohols. Wherein IA is alkali metal lithium, sodium or potassium, P is chlorine, bromine or acid radical. Furthermore, the heterogeneous solution may have a mass content of isobutene or a mixture of isobutene and further comonomers of from 5 to 50%.
According to the invention, said coinitiators are preferably chosen according to the general structural formula MXnOr AlR3-mXmWherein M is Al, Ti or Fe, X is a halogen atom, R is C with or without halogen or nitro derivative substitution2-C10Is alkyl, aryl, arylalkyl or alkylaryl, m is 1, 2 or 3, and n is 3 or 4. Wherein, the MXnCan be selected from AlCl3、TiCl4And FeCl3At least one of (A), the AlR3-mXmCan be selected from Al (C)2H5)Cl2、Al(C2H5)2Cl、Al(i-C4H9)Cl2、Al(i-C4H9)2Cl、Al(C2H5)1.5Cl1.5And Al (i-C)4H9)1.5Cl1.5At least one of (1).
According to the present invention, the electron donor is preferably at least one of an alcohol compound, a phenol compound and an ester compound. Specific examples of the alcohol compound include, but are not limited to: methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, tert-butanol, n-pentanol, isopentanol, quaternary pentanol, n-hexanol, n-heptanol, n-octanol, 2-dimethylpropanol, 2, 3-dimethyl-2-butanol, 3-dimethyl-2-butanol, 2-ethylbutanol, 2-methylpentanol, 3-ethyl-2-pentanol, 2, 4-dimethylpentanol, 2-methyl-2-hexanol, 2-ethylbutanol, 2, 3-dimethylpentanol, 2, 4-dimethylpentanol, 2,3, 4-trimethyl-3-pentanol, 2-methyl-3-ethylpentanol, 3, 4-dimethylhexanol, 3-methylheptanol, 2-propylpentanol, At least one of 2-ethylhexanol, dimethylheptanol, nonanol, decanol, linalool, benzyl alcohol, p-tolylmethanol, and phenethyl alcohol. Specific examples of the phenolic compound include, but are not limited to: at least one of phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2-ethylphenol, 2, 6-di-t-butylphenol and 2, 6-di-t-butyl-4-methylphenol. Specific examples of the ester compound include, but are not limited to: methyl acetate, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, methyl acrylate, methyl methacrylate, methyl benzoate, methyl hydroxybenzoate, ethyl benzoate, ethyl hydroxybenzoate, propyl benzoate, allyl benzoate, propyl hydroxybenzoate, butyl benzoate, butyl hydroxybenzoate, octyl hydroxybenzoate, methyl toluate, ethyl phenylacetate, isobutyl phenylacetate, methyl hydroxyphenylacetate, ethyl hydroxyphenylacetate, dodecyl hydroxybenzoate, hexadecyl trihydroxybenzoate, n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, methyl hydroxyphenylpropionate, ethyl hydroxyphenylpropionate, 3, 5-bis (1, 1-dimethylethyl) -4-hydroxyphenylpropionate, butyl acetoacetate, methyl methacrylate, methyl propionate, ethyl propionate, butyl benzoate, at least one of diallyl phthalate and diisooctyl phthalate.
The vinyl chloride resin may be commercially available or may be prepared by various methods known in the art. The vinyl chloride resin is a product of suspension polymerization, emulsion polymerization or bulk polymerization of vinyl chloride, and the solid is preferably in the form of particles or powder, and the particle diameter thereof is preferably 0.1 μm or more, more preferably 0.2 to 500 μm, further preferably 0.3 to 400 μm, and most preferably 0.5 to 370 μm.
According to the invention, the temperature of the heterogeneous polymerization reaction is preferably-100 to 25 ℃, more preferably-95 to 15 ℃, and most preferably-90 to 5 ℃; the time is 1-150 min, more preferably 2-90 min, and most preferably 3-40 min.
The method for preparing the vinyl chloride resin composite further comprises: and after the heterogeneous polymerization reaction is finished, adding alcohol substances, ammonia, amine substances or water into the reaction system to terminate the polymerization reaction, adding alcohol substances or water to precipitate a polymer, and drying to obtain the vinyl chloride resin compound. The alcohol or water is usually in excess. The alcohol includes, but is not limited to, ethanol.
The present invention also provides a vinyl chloride resin composite prepared by the above method.
The present invention will be described in detail below by way of examples.
(1) The weight average molecular weight (M) of the polymer was determined by gel chromatography GPCw) And molecular weight distribution index (M)w/Mn) Tetrahydrofuran was used as the mobile phase at a flow rate of 1 mL/min.
(2) Measurement of composition content of vinyl chloride resin composite: the total mass content of the isobutylene-based polymer segment branches in the vinyl chloride resin composite was measured by FTIR method.
(3) Thermal stability measurement of vinyl chloride resin composite: the thermal decomposition temperature of the compound was measured by TAQ50 thermogravimetric analyzer (TGA) in the range of 50-600 deg.C under nitrogen atmosphere.
(4) Mechanical property test of vinyl chloride resin compound: and preparing a sample according to GB/T1040-2006 Plastic tensile property test method, and testing the mechanical property of the composite material by adopting a universal material testing machine.
(5) Airtightness test of vinyl chloride resin composite: the oxygen transmission coefficient of the composite material is characterized by adopting a VAC-V2 differential pressure method gas permeameter at 23 ℃. The smaller the oxygen transmission coefficient, the better the airtightness of the material.
Example 1
150g of PVC (M) in the solid state are added to the reaction vesselw98kg/mol of a polymer with PDI of 1.8 and a particle size of 20-170 mu m, adding 400mL of precooled isobutene/hexane solution, adding 400mL of an aqueous phase medium (specifically, the mass ratio of sodium chloride, potassium chloride and lithium chloride to water is 1:1:22:76), and stirring to form a heterogeneous system; the heterogeneous system and FeCl-containing3Mixing with isopropanol system, wherein PVC, FeCl3The molar ratio of isopropanol to isobutene was 4.5X 10-3：5.1×10-2：7.1×10-2: 1. the polymerization temperature is-75 ℃, and 50mL of water is added after 5min of polymerization reaction to terminate the reaction; after the reaction system is stopped, washing the reaction system by water and hexane in sequence, and repeating the washing for three times to obtain the PVC/PVC-g-PIB compound. And (2) drying in vacuum at 40 ℃ to obtain a dried PVC/PVC-g-PIB compound, wherein the PVC/PVC-g-PIB compound comprises polyvinyl chloride particles and a polyvinyl chloride graft copolymer coated on the surfaces of the polyvinyl chloride particles, the polyvinyl chloride graft copolymer is a polymer of which a polyvinyl chloride main chain is connected with a plurality of isobutylene-based polymer chain forged branches, and the total mass content of the isobutylene-based polymer chain forged branches is 14 wt%.
The prepared PVC/PVC-g-PIB compound has the tensile strength of 44MPa and the elongation at break of 28 percent. Compared with the PVC of the comparative example 1, the PVC material has obviously improved tensile strength and elongation at break, so that the PVC material has the effects of strengthening and toughening, and thus the in-situ strengthening and toughening of the PVC material are realized, and the performance of the material is improved.
The 5% weight loss of the prepared PVC/PVC-g-PIB compound corresponds to a decomposition temperature of 278 ℃, and compared with the PVC of comparative example 1, the thermal stability of the compound is improved by 25 ℃.
The oxygen transmission coefficient of the prepared PVC/PVC-g-PIB compound is 2.17 multiplied by 10-15cm3·cm/cm2s.Pa, an air-tightness improved by 20 times compared with the PVC of comparative example 1.
Example 2
150g of solid PVC (specifically same as in example 1), 400mL of precooled isobutylene/hexane solution and 400mL of aqueous phase medium (specifically same as in example 1) are sequentially added into a reaction vessel to form a heterogeneous system; the heterogeneous system and the catalyst containing AlCl3And 3, 5-di-tert-butyl-4-hydroxybenzoic acid n-hexadecyl ester (B), wherein the PVC and the AlCl are mixed3B to isobutene in a molar ratio of 4.5X 10-3：1.0×10-2：3.0×10-3: 1. the polymerization temperature was-75 ℃ and the polymerization was terminated after 5 min. The polymer working-up procedure was as in example 1 to give a dried PVC/PVC-g-PIB compound in which the total content by mass of the chain branches of the isobutylene-based polymer was 34% by weight.
The prepared PVC/PVC-g-PIB compound has the tensile strength of 35MPa and the elongation at break of 45 percent. Compared with the PVC of the comparative example 1, the PVC has obviously improved tensile strength and elongation at break, so that the PVC has the effects of strengthening and toughening (see figure 1), thereby realizing in-situ strengthening and toughening of the PVC material, obviously improving the performance of the material, and obviously having the performance superior to the corresponding performance of the blend of the PVC and the PIB (comparative example 2).
The 5% weight loss of the prepared PVC/PVC-g-PIB compound corresponds to a decomposition temperature of 295 ℃, and compared with the PVC of comparative example 1, the thermal stability of the compound is improved by 42 ℃.
The oxygen transmission coefficient of the prepared PVC/PVC-g-PIB compound is 3.51 multiplied by 10-15cm3·cm/cm2s.Pa, the airtightness was improved by 12 times as compared with the PVC of comparative example 1.
Example 3
3g of solid PVC (specifically same as example 1), 20mL of precooled isobutylene/hexane solution and 20mL of aqueous phase medium (specifically same as example 1) are sequentially added into a reaction vessel to form a heterogeneous system; the heterogeneous system is mixed with a mixture containing ethyl aluminum dichloride (E) and n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoic acid(B) Wherein the molar ratio of PVC, E, B to isobutene is 1.8X 10-3：8.0×10-3：8.0×10-4: 1. the polymerization temperature was-65 ℃ and the polymerization was terminated after 150 min. The polymer working-up procedure was as in example 1 to give a dried PVC/PVC-g-PIB compound in which the total content by mass of the chain branches of the isobutylene-based polymer was 17% by weight.
The prepared PVC/PVC-g-PIB compound has the tensile strength of 41MPa and the elongation at break of 32 percent. Compared with the PVC of the comparative example 1, the PVC material has obviously improved tensile strength and elongation at break, so that the PVC material has the effects of strengthening and toughening, and thus the in-situ strengthening and toughening of the PVC material are realized, and the performance of the material is obviously improved.
The 5% weight loss of the prepared PVC/PVC-g-PIB compound corresponds to a decomposition temperature of 288 ℃, and compared with the PVC of comparative example 1, the thermal stability is improved by 35 ℃.
The oxygen transmission coefficient of the prepared PVC/PVC-g-PIB compound is 2.51 multiplied by 10-15cm3·cm/cm2s.Pa, an air-tightness improved by 17 times compared with the PVC of comparative example 1.
Example 4
3g of solid PVC (specifically same as in example 1), 20mL of precooled isobutylene/hexane solution and 20mL of aqueous phase medium (specifically same as in example 1) are sequentially added into a reaction vessel to form a heterogeneous system; the heterogeneous system and FeCl-containing3Mixing with isopropanol system, wherein PVC, FeCl3The molar ratio of isopropanol to isobutene was 4.5X 10-3：4.5×10-2：6.3×10-2: 1. the polymerization temperature was-60 ℃ and the polymerization was terminated after 20 min. The polymer working-up procedure was as in example 1 to give a dried PVC/PVC-g-PIB compound in which the total content by mass of the chain branches of the isobutylene-based polymer was 12% by weight.
The prepared PVC/PVC-g-PIB compound has the tensile strength of 46MPa and the elongation at break of 24 percent. Compared with the PVC of the comparative example 1, the PVC material has obviously improved tensile strength and elongation at break, so that the PVC material has the effects of strengthening and toughening, and thus the in-situ strengthening and toughening of the PVC material are realized, and the performance of the material is improved.
The 5% weight loss of the prepared PVC/PVC-g-PIB compound corresponds to the decomposition temperature of 272 ℃, compared with the PVC of comparative example 1, the 5% weight loss corresponds to the decomposition temperature of 19 ℃, and the thermal stability of the compound is improved.
The oxygen transmission coefficient of the prepared PVC/PVC-g-PIB compound is 3.88 multiplied by 10-15cm3·cm/cm2s.Pa, an increase in airtightness of 11 times as compared with the PVC of comparative example 1.
Example 5
150g of solid PVC (same as in example 1), 400mL of precooled isobutylene/hexane solution and 400mL of aqueous phase medium (same as in example 1) are sequentially added into a reaction vessel to form a heterogeneous system; the heterogeneous system and the catalyst containing AlCl3Mixing with a system of B, wherein PVC, AlCl3B to isobutene in a molar ratio of 4.5X 10-3：1.0×10-2：3.0×10-3: 1. the polymerization temperature was-62 ℃ and the polymerization was terminated after 5 min. Polymer work-up As in example 1, a PVC/PVC-g-PIB compound was obtained in which the total content by mass of the chain branches of the isobutylene-based polymer segment was 24% by weight.
The prepared PVC/PVC-g-PIB compound has the tensile strength of 32MPa and the elongation at break of 36 percent. Compared with the PVC of the comparative example 1, the PVC has obviously improved tensile strength and elongation at break, so that the PVC material has the effects of strengthening and toughening, realizes in-situ strengthening and toughening of the PVC material, improves the performance of the material, and has the performance obviously superior to the mechanical performance of a PIB/PVC blend (the content of PIB is 20 percent) (the comparative example 3).
The 5% weight loss of the prepared PVC/PVC-g-PIB compound corresponds to a decomposition temperature of 287 ℃, and compared with the PVC of comparative example 1, the thermal stability of the compound is improved by 35 ℃.
The oxygen transmission coefficient of the prepared PVC/PVC-g-PIB compound is 2.48 multiplied by 10-15cm3·cm/cm2s.Pa, an air-tightness improved by 17 times compared with the PVC of comparative example 1.
Example 6
150g of solid PVC pellets (as in example 1) and 500mL of precooled isobutylene/hexane solution and 500mL of deionized water were added to the reaction vesselForming a heterogeneous system; the heterogeneous system and FeCl-containing3Mixing with isopropanol system, wherein PVC, FeCl3The molar ratio of isopropanol to isobutene was 4.5X 10-3：4.4×10-2：6.16×10-2: 1. the polymerization temperature was 0 ℃ and the polymerization was terminated after 10 min. The polymer working-up procedure was as in example 1 to give a dried PVC/PVC-g-PIB compound in which the total content by mass of the chain branches of the isobutylene-based polymer was 11% by weight.
The prepared PVC/PVC-g-PIB compound has the tensile strength of 42MPa and the elongation at break of 18 percent. Compared with the PVC of the comparative example 1, the PVC has obviously improved tensile strength and elongation at break, so that the PVC material has the effects of strengthening and toughening, and the in-situ strengthening and toughening of the PVC material are realized, the performance of the material is improved, and the performance is obviously superior to the corresponding performance of the blend of the PVC and the PIB (comparative example 2).
The 5% weight loss of the prepared PVC/PVC-g-PIB compound corresponds to a decomposition temperature of 279 ℃, and compared with the PVC of comparative example 1, the thermal stability of the compound is improved by 26 ℃.
The oxygen transmission coefficient of the prepared PVC/PVC-g-PIB compound is 4.02 multiplied by 10-15cm3·cm/cm2s.Pa, 10 times higher air tightness than the PVC of comparative example 1.
Example 7
150g of solid PVC pellets (M) are added to the reaction vesselw210kg/mol, PDI 2.3, particle size 120-; the heterogeneous system and FeCl-containing3Mixing with isopropanol system, wherein PVC, FeCl3The molar ratio of isopropanol to isobutene was 4.5X 10-3：4.4×10-2：6.16×10-2: 1. the polymerization temperature was-80 ℃ and the polymerization was terminated after 5 min. The polymer working-up procedure was as in example 1 to give a PVC/PVC-g-PIB composite in which the total content by mass of the chain branches of the isobutylene-based polymer chain was 14% by weight
The prepared PVC/PVC-g-PIB compound has the tensile strength of 39MPa and the elongation at break of 21 percent. Compared with the PVC of the comparative example 1, the PVC has obviously improved tensile strength and elongation at break, so that the PVC material has the effects of strengthening and toughening, and the in-situ strengthening and toughening of the PVC material are realized, the performance of the material is improved, and the performance is obviously superior to the corresponding performance of the blend of the PVC and the PIB (comparative example 2).
The 5% weight loss of the prepared PVC/PVC-g-PIB compound corresponds to a decomposition temperature of 289 ℃, and compared with the PVC of comparative example 1, the thermal stability of the compound is improved by 36 ℃.
The oxygen transmission coefficient of the prepared PVC/PVC-g-PIB compound is 3.08 multiplied by 10-15cm3·cm/cm2s.Pa, the airtightness was improved by 14 times as compared with the PVC of comparative example 1.
Example 8
150g of solid PVC (M) are added in succession to the reaction vesselw76kg/mol, PDI 2.1, particle size 20-200 μm) and 500mL of precooled isobutene/hexane solution to form a heterogeneous system; the heterogeneous system and FeCl-containing3Mixing with isopropanol system, wherein PVC, FeCl3The molar ratio of isopropanol to isobutene was 4.5X 10-3：4.4×10-2：6.16×10-2:1, the polymerization temperature is-80 ℃, and the polymerization reaction is terminated after 5 min. Polymer work-up the procedure is as in example 1, giving a PVC/PVC-g-PIB compound in which the total content by mass of chain branches of the isobutylene-based polymer chain is 12% by weight.
The prepared PVC/PVC-g-PIB compound has the tensile strength of 35MPa and the elongation at break of 11 percent. Compared with the PVC of the comparative example 1, the PVC has obviously improved tensile strength and elongation at break, so that the PVC has the effects of strengthening and toughening, the in-situ strengthening and toughening of the PVC material are realized, the material performance is improved, and the performance is obviously superior to the corresponding performance of the blend of the PVC and the PIB (comparative example 2).
The 5% weight loss of the prepared PVC/PVC-g-PIB compound corresponds to a decomposition temperature of 297 ℃, and compared with the PVC of comparative example 1, the thermal stability of the compound is improved by 44 ℃.
The oxygen transmission coefficient of the prepared PVC/PVC-g-PIB compound is 3.56 multiplied by 10-15cm3·cm/cm2s.Pa, the airtightness was improved by 12 times as compared with the PVC of comparative example 1.
Example 9
20g of solid PVC (M) are added in succession to the reaction vesselw335kg/mol, PDI 3.0, particle size 0.1-2 μm) and 100mL of precooled isobutene/hexane solution, forming a heterogeneous system; then with FeCl3Mixing with isopropanol system, wherein PVC, FeCl3The molar ratio of isopropanol to isobutene was 4.5X 10-3：2.0×10-2：2.8×10-2: 1. the polymerization temperature was-80 ℃ and the polymerization was terminated after 5 min. Polymer work-up the procedure is as in example 1, giving a PVC/PVC-g-PIB compound in which the total content by mass of chain branches of the isobutylene-based polymer chain is 20% by weight.
Comparative example 1
The solid PVC particles (same as example 1) are used for preparing a film material, and mechanical property test is carried out, wherein the tensile strength is 32MPa, and the elongation at break is 2%.
The 5% weight loss of the PVC corresponds to a thermal decomposition temperature of 253 ℃.
The PVC has an oxygen transmission coefficient of 42.9X 10-15cm3·cm/cm2·s·Pa。
Comparative example 2
Solid PVC pellets (same as example 1) were mixed with PIB (M)w138kg/mol) according to the mass ratio of 7:3, and blending by a double-screw extruder at the mixing temperature of 180 ℃ and the screw rotating speed of 50r/min to obtain the PVC/PIB binary blend, wherein the mass fraction of the PIB is 30%. The tensile strength was 9.4MPa and the elongation at break was 7%.
Comparative example 3
And (3) blending the solid PVC particles (same as example 1) and the PIB (same as comparative example 2) by a double-screw extruder according to the mass ratio of 8:2, wherein the mixing temperature is 180 ℃, the screw rotating speed is 50r/min, and the PVC/PIB binary blend is obtained, wherein the mass fraction of the PIB is 20%. The tensile strength was 12.5MPa and the elongation at break was 5%.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. A vinyl chloride resin composite comprising a solid vinyl chloride resin and a vinyl chloride resin graft copolymer coated on the surface of the vinyl chloride resin, wherein the vinyl chloride resin is at least one selected from the group consisting of polyvinyl chloride, chlorinated polyvinyl chloride and a copolymer of vinyl chloride and vinyl acetate, the vinyl chloride resin graft copolymer is a polymer having a main chain of polyvinyl chloride, chlorinated polyvinyl chloride or a copolymer of vinyl chloride and vinyl acetate and having a plurality of chain branches of an isobutylene-based polymer segment connected thereto, and the total mass content of the chain branches of the isobutylene-based polymer segment is 5 to 50 wt%, preferably 7 to 45 wt%, more preferably 9 to 40 wt%, based on the total mass of the vinyl chloride resin composite.
2. The vinyl chloride resin composite according to claim 1, wherein the isobutylene-based polymer segment branch is an isobutylene homo-segment or a copolymerized segment of isobutylene and other comonomers; when the chain segment branch of the isobutylene-based polymer is a copolymerization segment of isobutylene and other comonomers, the molar content of isobutylene structural units is 95.0 to 99.9 mol%; the other comonomer is conjugated diene and/or vinyl aromatic hydrocarbon.
3. The vinyl chloride resin composite according to claim 1 or 2, wherein the polymer weight average molecular weight M of the vinyl chloride resinwFrom 50 to 400kg/mol, preferably from 60 to 380kg/mol, more preferably from 70 to 350 kg/mol; molecular weight distribution index Mw/MnIs 1.3 to 4.0, preferably 1.4 to 3.5, more preferably 1.5 to 3.2.
4. The vinyl chloride resin composite according to claim 1 or 2, wherein the vinyl chloride resin is in the form of particles or powder, and has a particle diameter of 0.1 μm or more, preferably 0.2 to 500 μm.
5. A method for preparing a vinyl chloride resin composite, the method comprising: vinyl chloride resins in solid form are polymerized heterogeneously with isobutene or with a mixture of isobutene and other comonomers in the presence of a coinitiator and an electron donor.
6. The production method according to claim 5,
the heterogeneous polymerization reaction method comprises the following steps:
A. mixing solid vinyl chloride resin with isobutene and other comonomers optionally contained to form a heterogeneous system, wherein the heterogeneous system contains or does not contain a reaction medium, the reaction medium is an organic solvent or an aqueous phase medium or contains both an organic solvent and an aqueous phase medium, and the organic solvent is an inert liquid organic matter which does not dissolve the solid vinyl chloride resin but can disperse or swell the solid vinyl chloride resin;
B. mixing the reaction system formed in the step A with a coinitiator and an electron donor to initiate heterogeneous polymerization;
preferably, the method further comprises: and after the heterogeneous polymerization reaction is finished, adding alcohol substances, ammonia, amine substances or water into the reaction system to terminate the polymerization reaction, adding alcohol substances or water to precipitate a polymer, and drying to obtain the vinyl chloride resin compound.
7. The production method according to claim 5 or 6, wherein the molar ratio of the vinyl chloride resin, the co-initiator, the electron donor and the isobutylene is (1.2 x 10)-3-6.0×10-3)：(5.0×10-3-8.0×10-2)：(6.0×10-4-8.0×10-2)：1；
Preferably, the coinitiator is selected according to the general structural formula MXnOr AlR3-mXmWherein M is Al, Ti or Fe, X is a halogen atom, and R is C with or without halogen or nitro-derived substitution2-C10M is 1, 2 or 3, n is 3 or 4; preferably, said MXnSelected from AlCl3、TiCl4And FeCl3At least one of (1), the AlR3-mXmSelected from Al (C)2H5)Cl2、Al(C2H5)2Cl、Al(i-C4H9)Cl2、Al(i-C4H9)2Cl、Al(C2H5)1.5Cl1.5And Al (i-C)4H9)1.5Cl1.5At least one of;
preferably, the electron donor is at least one of an alcohol compound, a phenol compound and an ester compound; the alcohol compound is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, n-pentanol, isopentanol, quaternary pentanol, n-hexanol, n-heptanol, n-octanol, 2-dimethylpropanol, 2, 3-dimethyl-2-butanol, 3-dimethyl-2-butanol, 2-ethylbutanol, 2-methylpentanol, 3-ethyl-2-pentanol, 2, 4-dimethylpentanol, 2-methyl-2-hexanol, 2-ethylbutanol, 2, 3-dimethylpentanol, 2, 4-dimethylpentanol, 2,3, 4-trimethyl-3-pentanol, 2-methyl-3-ethylpentanol, 3, 4-dimethylhexanol, 3-methylheptanol, heptanol, At least one of 2-propylpentanol, 2-ethylhexanol, dimethylheptanol, nonanol, decanol, linalool, benzyl alcohol, p-tolyl methanol, and phenethyl alcohol; the phenolic compound is selected from at least one of phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2-ethylphenol, 2, 6-di-tert-butylphenol and 2, 6-di-tert-butyl-4-methylphenol; the ester compound is selected from methyl acetate, methyl acetoacetate, ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, methyl acrylate, methyl methacrylate, methyl benzoate, methyl hydroxybenzoate, ethyl benzoate, ethyl hydroxybenzoate, propyl benzoate, allyl benzoate, propyl hydroxybenzoate, butyl benzoate, butyl hydroxybenzoate, octyl hydroxybenzoate, methyl toluate, ethyl phenylacetate, isobutyl phenylacetate, methyl hydroxybenzoate, ethyl hydroxybenzoate, dodecyl hydroxybenzoate, hexadecyl hydroxybenzoate, n-hexadecyl 3, 5-di-tert-butyl-4-hydroxybenzoate, methyl hydroxyphenylpropionate, ethyl hydroxyphenylpropionate, 3, 5-di (1, 1-dimethylethyl) -4-hydroxyphenylpropionate, butyl hydroxybenzoate, methyl methacrylate, ethyl hydroxybenzoate, ethyl methacrylate, ethyl hydroxybenzoate, ethyl methacrylate, methyl methacrylate, ethyl hydroxybenzoate, butyl methacrylate, ethyl hydroxybenzoate, methyl methacrylate, ethyl hydroxybenzoate, at least one of diallyl phthalate and diisooctyl phthalate.
8. The production method according to claim 5 or 6, wherein the vinyl chloride resin is in the form of particles having a particle diameter of 0.1 μm or more, preferably 0.2 to 500 μm.
9. The preparation method according to claim 5 or 6, wherein the temperature of the heterogeneous polymerization reaction is-100 to 25 ℃, preferably-95 to 15 ℃, and more preferably-90 to 5 ℃; the time is 1-150 min, preferably 2-90 min, and more preferably 3-40 min.
10. A vinyl chloride resin composite prepared by the method of any one of claims 5 to 9.
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