CN109485795B - Copolymer compatilizer and preparation method and application thereof - Google Patents
Copolymer compatilizer and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a copolymer compatilizer, which comprises the following components in percentage by weight: solubility parameter is 16.5-23(MPa)1/250-80 wt% of m-alkenyl monomer, 0.1-10 wt% of functional monomer, 10-40 wt% of functionalized liquid polybutadiene, and the structure is shown as the following formula:
in the formula R1represents-H or-COOH; r2represents-H or-CH3(ii) a X represents-OH, -COOH or-NH2One kind of (1). The number n of the repeating units is an integer of 10 to 200. The invention also provides a preparation method and application thereof. Compared with the prior art, the terpolymer disclosed by the invention can be stably distributed on a two-phase interface of polyester or polyamide and ABS, the phase morphology can be improved, and the mechanical property, especially the impact property, of the alloy can be improved.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a copolymer compatilizer, a preparation method and application thereof, which can be used for improving compatibility and improving the performance of a blending material.
Background
The polymer alloy technology can improve the performance of polymer materials, reduce production conditions, realize the functionalization and high performance of the polymer materials, and play an irreplaceable role in the fields of polymer science and polymer material engineering.
It is generally believed that in order to ensure good blending effect, the following principles should be considered when selecting the resin for good compatibility of each component of the polymer alloy: the principle of polarity matching, the principle of similar surface tension, the principle of similar diffusion capacity, the principle of equal viscosity and the principle of similar solubility parameter. Research shows that the conditions are difficult to meet at the same time in general, and in actual production, a mode of adding a compatilizer is often adopted to improve the compatibility of the alloy.
Comb-like copolymers are polymers in comb-like shape formed by simultaneously grafting a plurality of linear branches onto a main chain, and are polymers with special properties. The comb copolymer can be obtained by copolymerizing short side-group monomers and long side-group monomers and can also be obtained by grafting side chains on a linear copolymer.
The compatibilizer functions to lower the surface tension of the two phases and to increase the degree of compatibility. Molecules with similar solubility parameters need to be considered in designing a compatibilizer.
The solubility parameter is a parameter for characterizing polymer-solvent interaction, the cohesive property of a substance can be quantitatively characterized by cohesive energy, the cohesive energy per unit volume becomes cohesive energy density, and the square root of the cohesive energy is the solubility parameter. Is calculated by the formula
Where δ is the solubility parameter, Δ E is the molar cohesive energy, V is the molar volume, and Δ E/V is the cohesive energy density.[1]
The solubility parameter of the small molecular solvent is calculated by a Clapeyron-clausius formula, and the solubility parameter of the polymer can be obtained by a viscosity method, a swelling degree method or direct calculation.
The compatibilizers described in this patent are prepared by solution polymerization, which is a polymerization reaction of monomers and initiators in a suitable solvent. The solution polymerization system has low viscosity, easy mixing and heat transfer, easy temperature control, reduced gel effect and no local overheat.
The compatibilizer molecule with side chains can improve the compatibility of the polyester or polyamide with ABS in high polymer blends.
Most of the compatilizers used at present are linear structures, and are easy to enrich in a certain phase of the alloy under the action of shearing force in the processing process of an extruder, so that the effect of the compatilizers on an interface is lost, and the use efficiency of the compatilizers is reduced.
Patent CN 1397573a discloses a liquid polybutadiene grafted unsaturated dicarboxylic acid copolymer and a preparation method thereof, wherein the copolymer can improve the glossiness and mechanical strength of thermoplastic elastomers or improve the strength and hardness of rubber products. However, the graft ratio of the polymer is low, and the polymer is easy to migrate into a rubber phase in the process of modifying and using the polymer, so that the interfacial activity is lost.
Patent CN101851321 discloses a terpolymer having a compatible main chain and reactive side groups, which can be applied to compatibilizers and matting agents. However, such linearly structured compatibilizers also suffer from the disadvantage of being easily migratable during processing.
[1] Homanjun, Physics of macromolecules, 2008, Press of the university of Compound Dan, p 52.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the compatilizer which is reasonable in preparation process, convenient to use and excellent in performance.
The purpose of the invention can be realized by the following technical scheme: a copolymer compatilizer, in particular a comb-shaped copolymer compatilizer, is obtained by polymerizing the following components in parts by weight:
1) solubility parameter is 16.5-23(MPa)1/2Preferably 17.4-23(MPa)1/250 to 80wt%, preferably 55 to 75wt%,
2) 0.1 to 10wt%, preferably 0.5 to 7wt%,
3) 10-40 wt%, preferably 18-38 wt%, of functionalized liquid polybutadiene having the structure shown by the following formula:
in the formula R1represents-H or-COOH; r2represents-H or-CH3(ii) a X represents-OH, -COOH or-NH2One of (1);
the number n of repeating units is an integer from 10 to 200, more preferably an integer from 10 to 100, where the wt.% is based on the total weight of monomers 1), 2) and 3).
The solubility parameter is 16.5-23(MPa)1/2Alkene of (A) and (B)The base monomer can be one or more selected from methacrylate monomers or acrylate monomers, can be one or more selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, hydroxyethyl methacrylate, 2-ethylhexyl acrylate and 2-hydroxypropyl acrylate, and can be further preferably one or more selected from methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate and butyl acrylate.
The functional monomer is one or more of mono-alkenyl dianhydride, mono-alkenyl isocyanate or mono-alkenyl epoxy monomer, and one or two of maleic anhydride and glycidyl methacrylate can be preferably selected.
The number average molecular weight of the polymer of the present invention is generally in the range of 3 to 12 ten thousand, preferably 4 to 8 ten thousand, as measured by GPC.
The invention further provides a preparation method of the compatilizer, which adopts a solution polymerization process to prepare the compatilizer, and comprises the following steps:
(1) adding a solvent and all monomers into a reaction kettle, and uniformly mixing;
(2) adding an oil-soluble initiator into a reaction system, heating to 50-120 ℃ under stirring, and reacting for 5-24 hours;
(3) and after the reaction is finished, removing the solvent and unreacted monomers to obtain a product.
The oil-soluble initiator is azo initiator or organic peroxy initiator, and can be selected from azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, cumene hydroperoxide, tert-butyl hydroperoxide, di-tert-butyl peroxide, dibenzoyl peroxide, dicumyl peroxide, lauroyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxypivalate, diisopropyl peroxydicarbonate and dicyclohexyl peroxydicarbonate. One or more of azobisisobutyronitrile, dibenzoyl peroxide, or dicumyl peroxide may be particularly preferred.
In the present invention, the weight of the initiator is 0.1 to 3wt% of the total mass of the monomers, and more preferably 0.5 to 2 wt%.
The solvent is one or more of aromatic hydrocarbon, aliphatic hydrocarbon, halogenated hydrocarbon, ketone, ether and ester solvents, can be one or more of tetrahydrofuran, dimethyl sulfoxide, cyclohexane, cyclohexanone, chloroform, toluene, xylene, benzene, dioxane, ethyl acetate, acetone, butanone and the like, and can be one or more of tetrahydrofuran, benzene, toluene, xylene and ethyl acetate. The amount of the solvent is such that the solid content of the solution polymerization system is 10 to 60wt%, and more preferably 25 to 50 wt%.
The reaction temperature is preferably 70-100 ℃, and the reaction time is preferably 7-14 hours.
Further, step (3) may comprise precipitation, filtration and drying (e.g., drying at 100 ℃ C. and 150 ℃ C.).
The products obtained according to the invention are generally comb-structured.
The invention further provides the application of the compatilizer in processing resin blend materials (such as blend materials of PC/ABS, PET/ABS, PA/ABS and the like). The compatilizer can be used for processing various blending materials such as PC/ABS, PET/ABS, PA/ABS and the like, improves the compatibility and improves the material performance.
Drawings
FIG. 1 is an infrared spectrum of a copolymer in example 1 of the present invention, and epoxy group absorption peaks of glycidyl methacrylate in FIG. 1 are 1239cm-1，911cm-1And 840cm-1(ii) a The carbonyl absorption peak of methyl methacrylate is 1723cm-1(ii) a The double bond absorption peak of polybutadiene was 987cm-1。
FIG. 2 is a DSC of example 1 of the present invention, in FIG. 2, the glass transition temperature at 100 ℃ is the glass transition temperature of the compatibilizer backbone methyl methacrylate, and the glass transition temperature at-101 ℃ is the glass transition temperature of the polybutadiene side chains.
FIG. 3 is a scanning electron micrograph of example 1 and comparative example 1 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples, which, however, are to be understood as being for the purpose of illustration only and not to be construed as limiting in any way.
Preparation of functionalized liquid polybutadiene
Preparation example 1
Adding a certain amount of carboxyl-terminated liquid polybutadiene (Shandong Qinlong chemical Co., Ltd., the number of repeating units is 100) and equimolar amount of glycidyl acrylate into a reaction kettle, then adding 4-dimethylaminopyridine which is a catalyst accounting for 3% of the total mass of reactants and toluene which is a solvent in a mass ratio of 1:1 to the total mass of the reactants into the reaction kettle, uniformly mixing, heating to 100 ℃ under stirring, and reacting for 5 hours. Then discharging, and removing the solvent, unreacted reactants and catalyst. The product obtained is dried at 120 ℃ to constant weight, giving example 1 functionalized liquid polybutadiene.
Preparation example 2
Adding a certain amount of hydroxyl-terminated liquid polybutadiene (50 in the number of repeating units, available from Shandong Qinlong chemical Co., Ltd.) and glycidyl methacrylate into a reaction kettle, wherein the ratio of the hydroxyl-terminated liquid polybutadiene to the glycidyl methacrylate is 1:1.2, then adding 4-dimethylaminopyridine which is a catalyst accounting for 4% of the total mass of reactants and cyclohexane which is a solvent accounting for 3:2 of the total mass of the reactants into the reaction kettle, uniformly mixing, heating to 110 ℃ under stirring, and reacting for 4 hours. Then discharging, and removing the solvent, unreacted reactants and catalyst. The resulting product was dried to constant weight at 120 ℃ to give functionalized liquid polybutadiene example 2.
Preparation example 3
A certain amount of hydroxyl-terminated liquid polybutadiene (30 in the number of repeating units, Shandong Qinlong chemical Co., Ltd.) and maleic anhydride were added to a reaction vessel, wherein the ratio of the hydroxyl-terminated liquid polybutadiene to the maleic anhydride was 1: 1.1. Then adding catalyst pyridine accounting for 6% of the total mass of the reactants and solvent cyclohexane in a mass ratio of 2:1 to the total mass of the reactants into a reaction kettle, uniformly mixing, heating to 110 ℃ under stirring, and reacting for 4 hours. Then discharging, and removing the solvent, unreacted reactants and catalyst. The resulting product was dried to constant weight at 120 ℃ to give functionalized liquid polybutadiene example 3.
Other functionalized liquid polybutadienes used in the following examples were prepared as described above except that hydroxyl-terminated liquid polybutadienes having different numbers of repeating units, different acid anhydrides or acid esters were used.
Example 1
Methyl methacrylate accounting for 68 percent of the total mass of the monomers, glycidyl methacrylate accounting for 4 percent of the total mass of the monomers and functionalized liquid polybutadiene accounting for 28 percent of the total mass of the monomers are added into a reaction kettle.
Wherein the functionalized liquid polybutadiene has the following structure:
then, adding all oil-soluble initiator azobisisobutyronitrile accounting for 0.1 percent of the total mass of the monomers and solvent ethyl acetate with the total mass ratio of the initiator to the monomers being 1:1 into a reaction kettle, mixing uniformly, heating to 70 ℃ under stirring, and reacting for 20 hours. Then discharging into a storage tank, precipitating, filtering, and drying the obtained product at 150 ℃ to constant weight to obtain the final product compatilizer (1# compatilizer), wherein the molecular weight of the product is 10.3 ten thousand according to GPC measurement.
Example 2
Methyl methacrylate accounting for 60 percent of the total mass of the monomers, glycidyl methacrylate accounting for 2 percent of the total mass of the monomers and functionalized liquid polybutadiene accounting for 38 percent of the total mass of the monomers are added into a reaction kettle.
Wherein the functionalized liquid polybutadiene has the following structure:
then, adding all oil-soluble initiator dibenzoyl peroxide accounting for 0.8 percent of the total mass of the monomers and solvent toluene accounting for 55:45 of the total mass of the monomers into a reaction kettle, uniformly mixing, heating to 80 ℃ under stirring, and reacting for 10 hours. Then discharging into a storage tank, precipitating, filtering, and drying the obtained product at 150 ℃ to constant weight to obtain the final product compatilizer (2# compatilizer), wherein the molecular weight of the product is 7.3 ten thousand according to GPC measurement.
Example 3
Styrene accounting for 70 percent of the total mass of the monomers, glycidyl methacrylate accounting for 0.1 percent of the total mass of the monomers and functionalized liquid polybutadiene accounting for 29.9 percent of the total mass of the monomers are added into a reaction kettle.
Wherein the functionalized liquid polybutadiene has the following structure:
then, adding all oil-soluble initiator azodiisoheptonitrile accounting for 3% of the total mass of the monomers and solvent xylene in a mass ratio of 1:1 to the total mass of the monomers into a reaction kettle, uniformly mixing, heating to 120 ℃ under stirring, and reacting for 1 hour. Then discharging into a storage tank, precipitating, filtering, and drying the obtained product at 150 ℃ to constant weight to obtain the final product compatilizer (3# compatilizer), wherein the molecular weight of the product is 3.5 ten thousand according to GPC measurement.
Example 4
Methyl acrylate accounting for 74 percent of the total mass of the monomers, glycidyl methacrylate accounting for 2 percent of the total mass of the monomers and functionalized liquid polybutadiene accounting for 38 percent of the total mass of the monomers are added into a reaction kettle.
Wherein the functionalized liquid polybutadiene has the following structure:
subsequently, the total oil-soluble initiator azobisisobutyronitrile/azobisisoheptonitrile, which accounted for 1% of the total mass of the monomers, was added to the reaction kettle, wherein the ratio of azobisisobutyronitrile to azobisisoheptonitrile was 1:1. Then adding butanone, a solvent of which the mass ratio to the total mass of the monomers is 55:45, into the reaction kettle, uniformly mixing, heating to 60 ℃ under stirring, and reacting for 18 hours. Then discharging into a storage tank, precipitating, filtering, and drying the obtained product at 150 ℃ to constant weight to obtain the final product compatilizer (4# compatilizer), wherein the molecular weight of the product is 6.2 ten thousand according to GPC measurement.
Example 5
Adding ethyl acrylate accounting for 63% of the total mass of the monomers, glycidyl methacrylate accounting for 1% of the total mass of the monomers and functionalized liquid polybutadiene accounting for 36% of the total mass of the monomers into a reaction kettle.
Wherein the functionalized liquid polybutadiene has the following structure:
then, adding all oil-soluble initiator dibenzoyl peroxide accounting for 2% of the total mass of the monomers and solvent cyclohexanone in a mass ratio of 1:1 to the total mass of the monomers into a reaction kettle, uniformly mixing, heating to 100 ℃ under stirring, and reacting for 5 hours. Then discharging into a storage tank, precipitating, filtering, and drying the obtained product at 150 ℃ to constant weight to obtain the final product compatilizer (5# compatilizer), wherein the molecular weight of the product is 2.9 ten thousand according to GPC measurement.
Example 6
Adding ethyl methacrylate accounting for 80% of the total mass of the monomers, glycidyl methacrylate accounting for 10% of the total mass of the monomers and functionalized liquid polybutadiene accounting for 10% of the total mass of the monomers into a reaction kettle.
Wherein the functionalized liquid polybutadiene has the following structure:
in the formula R1represents-COOH; r2represents-H; x represents-COOH. The number of repeating units n is 10.
Subsequently, 1.2% of the total mass of the monomers of the oil-soluble initiator dibenzoyl peroxide and 3:2, adding the solvent toluene into the reaction kettle, uniformly mixing, heating to 110 ℃ under stirring, and reacting for 7 hours. Then discharging into a storage tank, precipitating, filtering, and drying the obtained product at 150 ℃ to constant weight to obtain the final product compatilizer (6# compatilizer), wherein the molecular weight of the product is 5.6 ten thousand according to GPC measurement.
Example 7
Butyl methacrylate accounting for 57 percent of the total mass of the monomers, glycidyl acrylate accounting for 3 percent of the total mass of the monomers and functionalized liquid polybutadiene accounting for 40 percent of the total mass of the monomers are added into a reaction kettle.
Wherein the functionalized liquid polybutadiene has the following structure:
subsequently, the total oil-soluble initiator azobisisobutyronitrile/dibenzoyl peroxide, which is 1% of the total mass of the monomers, was added to the reaction kettle, wherein the ratio of azobisisobutyronitrile to dibenzoyl peroxide was 1:1. And adding a mixed solvent with the total mass ratio of the mixed solvent to the monomers being 2:3 into the reaction kettle, wherein the mixed solvent is a combination of butanone and cyclohexanone with the mass ratio of 1: 2. The materials are mixed evenly and heated to 90 ℃ under stirring to react for 12 hours. Then discharging into a storage tank, precipitating, filtering, and drying the obtained product at 150 ℃ to constant weight to obtain the final product compatilizer (7# compatilizer), wherein the molecular weight of the product is 7.6 ten thousand according to GPC measurement.
Example 8
Tert-butyl methacrylate accounting for 73 percent of the total mass of the monomers, maleic anhydride accounting for 2 percent of the total mass of the monomers and functionalized liquid polybutadiene accounting for 25 percent of the total mass of the monomers are added into a reaction kettle.
Wherein the functionalized liquid polybutadiene has the following structure:
then, adding all oil-soluble initiator azobisisobutyronitrile accounting for 0.9 percent of the total mass of the monomers and solvent toluene with the total mass ratio of the azodiisobutyronitrile to the monomers being 9:1 into a reaction kettle, mixing uniformly, heating to 50 ℃ under stirring, and reacting for 24 hours. Then discharging into a storage tank, precipitating, filtering, and drying the obtained product at 150 ℃ to constant weight to obtain the final product compatilizer (8# compatilizer), wherein the molecular weight of the product is 7.5 ten thousand according to GPC measurement.
Example 9
Propyl methacrylate accounting for 62 percent of the total mass of the monomers, maleic anhydride accounting for 5 percent of the total mass of the monomers and functionalized liquid polybutadiene accounting for 33 percent of the total mass of the monomers are added into a reaction kettle.
Wherein the functionalized liquid polybutadiene has the following structure:
then, adding all oil-soluble initiator dibenzoyl peroxide accounting for 2.4 percent of the total mass of the monomers and solvent cyclohexane in a mass ratio of 45:55 to the total mass of the monomers into a reaction kettle, uniformly mixing, heating to 120 ℃ under stirring, and reacting for 2 hours. The product was then discharged into a holding tank, precipitated, filtered, and then dried to constant weight at 150 ℃ to give a final product compatibilizer (# 9 compatibilizer) having a molecular weight of 11.5 ten thousand as determined by GPC.
Example 10
Methyl methacrylate accounting for 54 percent of the total mass of the monomers, maleic anhydride accounting for 10 percent of the total mass of the monomers and functionalized liquid polybutadiene accounting for 36 percent of the total mass of the monomers are added into a reaction kettle.
Wherein the functionalized liquid polybutadiene has the following structure:
subsequently, the total oil-soluble initiator azobisisoheptonitrile/lauroyl peroxide, which is 1.2% of the total mass of the monomers, was added to the reaction kettle, wherein the ratio of azobisisoheptonitrile to lauroyl peroxide was 1:1. And adding a mixed solvent with the total mass ratio of the mixed solvent to the monomers being 1:1 into the reaction kettle, wherein the mixed solvent is a combination of benzene and toluene with the mass ratio of 1: 2. The materials are mixed evenly and heated to 80 ℃ under stirring to react for 10 hours. Then discharging into a storage tank, precipitating, filtering, and drying the obtained product at 150 ℃ to constant weight to obtain the final product compatilizer (10# compatilizer), wherein the molecular weight of the product is 8.2 ten thousand according to GPC measurement.
Example 11
Butyl acrylate accounting for 79 percent of the total mass of the monomers, maleic anhydride accounting for 3 percent of the total mass of the monomers and functionalized liquid polybutadiene accounting for 18 percent of the total mass of the monomers are added into a reaction kettle.
Wherein the functionalized liquid polybutadiene has the following structure:
then, adding all oil-soluble initiator dibenzoyl peroxide accounting for 1% of the total mass of the monomers and solvent trichloromethane with the total mass ratio of 45:55 into a reaction kettle, uniformly mixing, heating to 80 ℃ under stirring, and reacting for 14 hours. Then discharging into a storage tank, precipitating, filtering, and drying the obtained product at 150 ℃ to constant weight to obtain the final product compatilizer (11# compatilizer), wherein the molecular weight of the product is 2.3 ten thousand according to GPC measurement.
Example 12
Adding 65% of ethyl acrylate, 0.1% of maleic anhydride and 34.9% of functionalized liquid polybutadiene into a reaction kettle.
Wherein the functionalized liquid polybutadiene has the following structure:
then, adding all oil-soluble initiator azobisisobutyronitrile accounting for 0.48 percent of the total mass of the monomers and solvent tetrahydrofuran in a mass ratio of 2:3 to the total mass of the monomers into a reaction kettle, uniformly mixing, heating to 60 ℃ under stirring, and reacting for 24 hours. The product was then discharged into a holding tank, precipitated, filtered, and then dried to constant weight at 150 ℃ to give a final product compatibilizer (12# compatibilizer) having a molecular weight of 3.7 ten thousand as determined by GPC.
Example 13
Styrene accounting for 61 percent of the total mass of the monomers, maleic anhydride accounting for 0.5 percent of the total mass of the monomers and functionalized liquid polybutadiene accounting for 38.5 percent of the total mass of the monomers are added into a reaction kettle.
Wherein the functionalized liquid polybutadiene has the following structure:
then, adding all oil-soluble initiator azobisisobutyronitrile accounting for 0.8 percent of the total mass of the monomers and solvent cyclohexane in a mass ratio of 3:2 to the total mass of the monomers into a reaction kettle, uniformly mixing, heating to 70 ℃ under stirring, and reacting for 13 hours. The product was then discharged into a holding tank, precipitated, filtered, and then dried to constant weight at 150 ℃ to give a final product compatibilizer (13# compatibilizer) having a molecular weight of 3.1 ten thousand as determined by GPC.
Example 14
Methyl acrylate accounting for 68 percent of the total mass of the monomers, maleic anhydride accounting for 1 percent of the total mass of the monomers and functionalized liquid polybutadiene accounting for 31 percent of the total mass of the monomers are added into a reaction kettle.
Wherein the functionalized liquid polybutadiene has the following structure:
subsequently, 1.5 percent of the total mass of the monomers of the oil-soluble initiator dibenzoyl peroxide and a toluene/xylene mixed solvent with the total mass ratio of the monomers of 4:1 are added into a reaction kettle, wherein the mixed solvent is a combination of toluene and xylene with the mass ratio of 1: 2. The materials are mixed evenly and heated to 100 ℃ under stirring to react for 6 hours. The product was then discharged into a holding tank, precipitated, filtered, and then dried to constant weight at 150 ℃ to give a final product compatibilizer (14# compatibilizer) having a molecular weight of 5.3 ten thousand as determined by GPC.
The above preparation examples and examples illustrate only the terpolymer of the present invention and its preparation process, but they do not limit the scope of the present invention. Any modification and variation of the present invention based on the spirit and concept thereof is within the scope of the claims of the present invention.
Test examples
PC resin: a1225, melt index 20g/10min at 300 ℃/1.2kg, produced by Wanhua chemical group, Inc.;
ABS resin: 8391,220 ℃/10kg, the melt index is 25g/10min, wherein the butadiene content is 15%, the acrylonitrile content is 20%, the styrene content is 65%, and the product is produced by Shanghai Gaoqiao petrochemical company;
the components are proportionally placed into a high-speed mixer to be mixed for 1-5 minutes, discharging is carried out, and then a screw extruder is used for extrusion and granulation, wherein the processing temperature is 220-280 ℃, and the rotation number of a screw is 180-600 rpm.
Test examples 1 to 15 Each component amount (unit: kg)
Test examples 1 to 14 were compared with comparative test example 1, and the tensile strength and elongation at break were measured in accordance with ISO 527 standard; the notched impact strength was measured according to ISO 180, the melt index was measured according to ISO 1133, the temperature was measured at 260 ℃ and the load was 5 Kg. The molar amount of functional monomer per kg of compatibilizer is determined according to GB/T4612-2008 and ASTM D3644-2015 and the properties are compared as follows.
Comparison of test Performance
Claims (21)
1. A copolymer compatibilizer, characterized by being polymerized from the following components:
1) solubility parameter is 16.5-23(MPa)1/250-80 wt% of the alkenyl monomer,
2) 0.1 to 10wt% of a functional monomer,
3) 10-40 wt% of functionalized liquid polybutadiene, wherein the structure is shown as the following formula:
in the formula R1represents-H or-COOH; r2represents-H or-CH3(ii) a X represents-OH, -COOH or-NH2In the above-mentioned manner, the first and second substrates are,
the number of repeating units n is an integer from 10 to 200, where the wt.% are based on the total weight of monomers 1), 2) and 3).
2. The copolymer compatibilizer of claim 1 wherein the following components are polymerized:
1) solubility parameter is 17.4-23(MPa)1/255 to 75wt% of the alkenyl monomer,
2) 0.5 to 7wt% of a functional monomer,
3) 18-38 wt% of functionalized liquid polybutadiene,
the number n of the repeating units is an integer of 10 to 100.
3. The copolymeric compatibilizer of claim 1, wherein the solubility parameter is from 16.5 to 23(MPa)1/2The alkenyl monomer is selected from one or more of methacrylate monomers or acrylate monomers.
4. The copolymeric compatibilizer of claim 3, wherein the solubility parameter is from 16.5 to 23(MPa)1/2The alkenyl monomer is one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, n-propyl acrylate, butyl acrylate, isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, hydroxyethyl methacrylate, 2-ethylhexyl acrylate and 2-hydroxypropyl acrylate.
5. The copolymeric compatibilizer of claim 4, wherein the solubility parameter is from 16.5 to 23(MPa)1/2The alkenyl monomer is one or more of methyl methacrylate, ethyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate and butyl acrylate.
6. The copolymer compatibilizer of claim 1 wherein said functional monomer is one or more of a monoalkenyl dianhydride, a monoalkenyl isocyanate, or a monoalkenyl epoxy monomer.
7. The copolymer compatibilizer of claim 6 wherein said functional monomer is one or both of maleic anhydride and glycidyl methacrylate.
8. A method for preparing the copolymer compatibilizer of any one of claims 1-7, comprising the steps of:
(1) adding all monomers into a reaction kettle, and uniformly mixing;
(2) adding an oil-soluble initiator and a solvent into a reaction system, heating to 50-120 ℃ under stirring, and reacting for 1-24 hours;
(3) and after the reaction is finished, removing the solvent and unreacted monomers to obtain a product.
9. The method of claim 8, wherein the oil-soluble initiator is one or more of azo initiators or organic peroxy initiators.
10. The method of claim 9, wherein the oil-soluble initiator is one or more selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, azobisisovaleronitrile, cumene hydroperoxide, t-butyl hydroperoxide, di-t-butyl peroxide, dibenzoyl peroxide, dicumyl peroxide, lauroyl peroxide, t-butyl peroxydibenzoate, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, and dicyclohexyl peroxydicarbonate.
11. The method of claim 10, wherein the oil-soluble initiator is one or more of azobisisobutyronitrile, dibenzoyl peroxide, or dicumyl peroxide.
12. The method according to any one of claims 8 to 11, wherein the weight of the initiator is 0.1 to 3wt% based on the total mass of the monomers.
13. The method according to claim 12, wherein the weight of the initiator is 0.5 to 2wt% based on the total mass of the monomers.
14. The method according to any one of claims 8 to 11, wherein the solvent is one or more of aromatic hydrocarbons, aliphatic hydrocarbons, halogenated hydrocarbons, ketones, ethers, and ester solvents.
15. The method according to claim 14, wherein the solvent is one or more of tetrahydrofuran, dimethylsulfoxide, cyclohexane, cyclohexanone, chloroform, toluene, xylene, benzene, dioxane, ethyl acetate, acetone, and methyl ethyl ketone.
16. The method according to claim 15, wherein the solvent is one or more of tetrahydrofuran, benzene, toluene, xylene, and ethyl acetate.
17. The method according to any one of claims 8 to 11, wherein the solid content of the solution polymerization system is 10 to 60 wt%.
18. The method according to claim 17, wherein the solid content of the solution polymerization system is 25 to 50 wt%.
19. The preparation method according to any one of claims 8 to 11, wherein the reaction temperature is 70 to 100 ℃; the reaction time is 1-14 hours.
20. Use of the copolymer compatibilizer defined in any one of claims 1 to 7 or obtained by the preparation method defined in any one of claims 8 to 19 for the processing of resin blend materials.
21. Use according to claim 20, characterized in that the resin blend material is a PC/ABS, PET/ABS, PA/ABS blend material.
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