CN104892805A - Preparation method of polyurethane grafted polystyrene aqueous dispersion - Google Patents

Preparation method of polyurethane grafted polystyrene aqueous dispersion Download PDF

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CN104892805A
CN104892805A CN201510306786.4A CN201510306786A CN104892805A CN 104892805 A CN104892805 A CN 104892805A CN 201510306786 A CN201510306786 A CN 201510306786A CN 104892805 A CN104892805 A CN 104892805A
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polystyrene
preparation
polyurethane
water dispersion
alcohol
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陈柏祥
马立翔
孙仪琳
李坚
任强
汪称意
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Changzhou University
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Changzhou University
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Abstract

The invention relates to a preparation method of a polyurethane grafted polystyrene aqueous dispersion. The preparation method comprises the steps of preparing hydroxyl-terminated polystyrene and preparing the polyurethane grafted polystyrene aqueous dispersion. The preparation method provided by the invention has the following beneficial effects: (1) the hydroxyl-terminated polystyrene is prepared by using an ARGET ATRP method, the structure, the molecular weight and the molecular weight distribution of the polymer can be controlled, the concentration dosage of a catalyst used in a reaction system is very low and can be reduced to tens of ppm or even lower, and meanwhile the sensitivity of the reactions system to the air is reduced; and (2) polystyrene is introduced into polyurethane to realize compatibility between the molecules of the polystyrene and the polyurethane, and the characteristics of waterborne polyurethane and styrene are integrated, so that the aqueous dispersion has the common excellent performances of the waterborne polyurethane and the styrene, and compared with the waterborne polyurethane, the polyurethane grafted polystyrene aqueous dispersion is effectively improved in mechanical property, water resistance and solvent resistance.

Description

A kind of preparation method of polyurethane grafted polystyrene water dispersion
Technical field
The invention belongs to chemical material field, relate to a kind of preparation method of polyurethane grafted polystyrene water dispersion.
Background technology
Urethane (Polyurethane is called for short PU) is that one reacts by polyisocyanates, polyvalent alcohol, organic molecule polyvalent alcohol (chainextender) the important macromolecular material made.It is made up of with hard section visibly different soft section of chemical property, and soft section is made up of oligomer polyol (normally polyether glycol and polyester polyol), and hard section is made up of polyisocyanates and small molecule chain extender.
Conventional urethane adopts organism to make solvent, often organic volatile material is obtained containing benzene class, ethers, aldehydes in product, these organism are explosive inflammable, the large and toxic contaminants environment of smell and the health of harm people, and working in this kind of environment for a long time can the health of grievous injury people.Aqueous polyurethane (WPU) just arises at the historic moment.Aqueous polyurethane (WPU) using water as dispersion medium, it not containing or organic solvent containing little amount, have do not fire, nontoxic, energy-conservation, easy storage, the advantage such as safety.Also maintain the advantage that solvent borne polyurethane is wear-resisting, low temperature resistant, antifatigue, snappiness are good simultaneously.
Polystyrene (Polystyrene is called for short PS), refers to the polymkeric substance synthesized through free radical polymerization by styrene monomer.It is a kind of water white thermoplastics, has the glass transition temp higher than 100 DEG C, is therefore often used to make the various one-trip container needing to bear the temperature of boiling water, and disposable foam food boxes etc.Ordinary polystyrene resin belongs to amorphous macromolecule polymkeric substance, the side base of polystyrene macromolecular chain is phenyl ring, large volume side base is the physicochemical property that the random arrangement of phenyl ring determines polystyrene, as transparency is high. and rigidity is large. and second-order transition temperature is high, and property is crisp.
The atom transfer radical polymerization (ATRP) proposed in nineteen ninety-five is gentle with reaction conditions, suitable monomers wide ranges, and molecular designing ability is strong and receive general attention, and is used to prepare acrylate based block copolymer.The subject matter of restriction ATRP mass-producing application is the metallic salt (most representative is cuprous halide) that ATRP gathers that required catalyzer is low-oxidation-state, easily oxidized, needs refining and consumption is very large before using.The use of a large amount of catalyzer not only increases cost, and removing and recycling of polymerization rear catalyst is also a masty problem, and industrialization difficulty is greatly not easily carried out.The appearance of transfer transport regenerated catalyst atom transfer radical polymerization (ARGET ATRP) solves the above-mentioned problem mentioned.Atom transfer radical polymerization is stepped again to industrialization go a step further.It in system, adds a kind of reductive agent as stannous octoate, xitix, glucose etc., and high-valence state metal complex a small amount of in system is constantly reduced to lower valency metal complex.Easily oxidized, consumption is large, removing difficulty can problem, facilitates the suitability for industrialized production of ATRP to it solve ATRP.
In the grafting method of existing urethane, disclose in CN102924692A " a kind of hypertonicity polyurethane grafted modified epoxy interpenetrating net polymer injection material and preparation method thereof ", it is with polyurethane grafted modified epoxy, provides a kind of preparation method of novel injection material.Disclose in CN1687166 " perfluoro olefin sulfonate grafted ion exchange resin of polystyrens and preparation method thereof ", the patent provides perfluoro olefin sulfonate grafted ion exchange resin of polystyrens and preparation method thereof.The preparation of polyurethane grafted polystyrene water dispersion is not all related in these methods.The present invention prepares terminal hydroxy group polystyrene by ARGET ATRP method, then terminal hydroxy group polystyrene graft is prepared polyurethane grafted polystyrene water dispersion on urethane.
Summary of the invention
The technical problem to be solved in the present invention is: based on the problems referred to above, the invention provides a kind of preparation method of polyurethane grafted polystyrene water dispersion.
The present invention solves the technical scheme that its technical problem adopts: a kind of preparation method of polyurethane grafted polystyrene water dispersion, comprises the following steps:
(1) preparation of terminal hydroxy group polystyrene: initiator, polystyrene, catalyzer, part, reductive agent and solvent I is joined in reaction vessel, reaction system is vacuumized, inflated with nitrogen 5min, 110 DEG C are reacted 0.5 ~ 10 hour, obtained terminal hydroxy group polystyrene, molecular weight distribution ﹤ 2.0;
(2) preparation of polyurethane grafted polystyrene water dispersion: hydrophilic chain extender, dibasic alcohol and trivalent alcohol are added in reaction vessel, is warming up to 100 ~ 150 DEG C, remove small molecules 5 ~ 15min; Then less than 65 DEG C are cooled to, add with the obtained terminal hydroxy group polystyrene of the step (1) of solvent II dissolving and vulcabond, be warming up to 80 ~ 95 DEG C, insulation reaction 2 ~ 5h, be cooled to room temperature, add solvent III adjusting viscosity, be cooled to less than 10 DEG C, add neutralizing agent adjust ph to 6 ~ 7; Finally the urethane of above-mentioned preparation-polystyrene performed polymer is joined in frozen water and disperse 3 ~ 6h, obtain polyurethane grafted polystyrene water dispersion.
Further, in step (1), initiator is an end group is Br, and another end group is organic bromo compound of hydroxyl, and organic bromo compound is alpha-brominated isopropylformic acid hydroxyl ethyl ester or alpha-brominated isopropylformic acid hydroxy butyl ester; Catalyzer is the transition metal halide CuCl of oxidation state 2, CuBr 2, FeCl 3or FeBr 3; Part is the one in five methyl diethylentriamine, hexamethyl three second tetramine, two (dimethyl aminoethyl) ether, bipyridine amine or three-(N, N-dimethyl aminoethyl) amine; Reductive agent is the one in stannous octoate, xitix or glucose; Solvent I is the one in toluene, methyl-phenoxide, DMF, tetrahydrofuran (THF), ethyl acetate or 1-Methyl-2-Pyrrolidone.
Further, polystyrene in step (1): the mol ratio of initiator is 20:1 ~ 500:1, polystyrene: the mol ratio of catalyzer is 1:0.0005 ~ 1:0.00005, catalyzer: the mol ratio of part is 1:10 ~ 1:30, catalyzer: the mol ratio of reductive agent is 1:10 ~ 1:25, and solvent I consumption is 50% of polystyrene quality.
Further, in step (2), hydrophilic chain extender is with one or more in the hydrophilic group dibasic alcohol of carboxyl, sulfonic group or tertiary amine groups, hydrophilic chain extender be dimethylol propionic acid, dihydroxyl half ester, dimethylolpropionic acid, N-tri-(methylol) methyl glycine, BDO-2-sodium sulfonate and derivative thereof, in one or more.
Further, in step (2), dibasic alcohol is the one in polyester diol, polyether Glycols, vinylformic acid dibasic alcohol, castor-oil plant oils dibasic alcohol, PCDL or polytetrahydrofuran dibasic alcohol; Trivalent alcohol is the one in polyester trivalent alcohol, polyether-tribasic alcohol, vinylformic acid trivalent alcohol, castor-oil plant oils trivalent alcohol, polycarbonate trivalent alcohol or polytetrahydrofuran trivalent alcohol.
Further, in step (2), vulcabond is diphenylmethanediisocyanate, tolylene diisocyanate, isophorone diisocyanate, naphthalene-1, one in 5-vulcabond, 2,6-vulcabond methyl caproates, 1,6-hexyl diisocyanate.
Further, in step (2), solvent II is the one in N-Methyl pyrrolidone, phenyl ether, methyl-phenoxide, toluene, dimethylbenzene, DMF, pimelinketone, butylacetate, dimethyl sulfoxide (DMSO).Solvent III is the one in acetone, butanone, methylethylketone, dioxane, N, N-dimethylformamide.
Further, in step (2), neutralizing agent is the one in triethylamine, dimethylethanolamine, diethanolamine, methylamine, ammoniacal liquor, sodium hydroxide or potassium hydroxide.
Further, step (2) middle vulcabond, dibasic alcohol, trivalent alcohol, hydrophilic chain extender, terminal hydroxy group polystyrene in step (2), feed intake according to mol ratio NCO/OH=0.5:1 ~ 4.0:1, hydrophilic chain extender quality account for vulcabond, dibasic alcohol, trivalent alcohol, hydrophilic chain extender, terminal hydroxy group polystyrene quality summation 4 ~ 8%, neutralizing agent consumption is 36% ~ 120% of hydrophilic chain extender molar mass, and terminal hydroxy group polystyrene and trivalent alcohol mol ratio are 1:1; The solid content of the polyurethane grafted polystyrene water dispersion of preparation is 5 ~ 30wt%.
The invention has the beneficial effects as follows: (1) utilizes ARGET ATRP method to prepare terminal hydroxy group polystyrene, can control the structure of polymkeric substance and molecular weight and molecular weight distribution, and catalyst concn consumption used in reaction system is very low, tens ppm can be dropped to even lower, reduce the susceptibility of reaction system to air simultaneously; (2) polystyrene is incorporated in urethane achieves that both are intermolecular compatible, combine the characteristic of aqueous polyurethane and styrenic, thus obtain having concurrently aqueous polyurethane and the common excellent properties of vinylbenzene, compared with aqueous polyurethane, the mechanical property of polyurethane grafted polystyrene water dispersion, water tolerance, solvent resistance are obtained for effective raising.
Embodiment
The invention will be further described in conjunction with specific embodiments now, and following examples are intended to the present invention instead of limitation of the invention further are described.
Embodiment 1
(1) molecular weight is the preparation of the terminal hydroxy group polystyrene of 5000
Vinylbenzene 150g, alpha-brominated isopropylformic acid hydroxy butyl ester 9.0759g (purity is 79%), CuBr is added in the four-hole boiling flask of 500mL that thermometer is housed 20.16086g, five methyl diethylentriamine 3.7336g, stannous octoate 7.2729g, methyl-phenoxide 75g, mechanical stirring Homogeneous phase mixing, the oxygen in bubbling 5min eliminating system, continues blistering reaction 3.5h in the oil bath pan of 110 DEG C, and transformation efficiency is 92%.Molecular weight Mn=5400 is recorded, molecular weight distribution PDI=1.23 with gel permeation chromatography GPC.This reacting middle catalyst consumption is the 500ppm of monomer molar amount, obtains molecular weight controlled, the polymkeric substance that molecular weight distribution is narrower.
(2) preparation of the polyurethane grafted polystyrene water dispersion of polystyrene/urethane=6% (mass ratio)
First 19g polyether Glycols (N220), 1g polyether-tribasic alcohol (N330), 1.6067g dimethylol propionic acid being added is equipped with in the four-hole boiling flask of stirring rake, is warming up to 120 DEG C and makes it to mix and get rid of small molecules.Then be cooled to 60 DEG C, add 5.8065g tolylene diisocyanate, 6.8g polystyrene solution (1.8g polystyrene, 5gN-methyl-2-pyrrolidone) controls its-NCO/-OH=1.5:1.Be warming up to 80 DEG C of reaction 3h.Cooling after terminating, room temperature adds 15g acetone regulation system viscosity.Add the neutralization of 0.9848g triethylamine, and be scattered in 50.462g water.Obtain urethane-polystyrene water dispersion that solid content is 20wt%.Wherein the ratio of N330 and polyether-tribasic alcohol mol ratio 1:1 adds, and makes the average functionality of monomer in reaction system be 2.
According to above method, prepare respectively polystyrene consumption account for urethane quality (urethane quality be N220, N330, polystyrene, dimethylol propionic acid, tolylene diisocyanate and triethylamine quality and) be the polyurethane polystyrene interpolymer water dispersion of 0wt%, 11wt%, 15wt%, 20wt%.
Embodiment 2
(1) molecular weight is the preparation of the terminal hydroxy group polystyrene of 7000
Vinylbenzene 156g, alpha-brominated isopropylformic acid hydroxy butyl ester 6.7421g (purity is 79%), CuBr is added in the four-hole boiling flask of 500mL that thermometer is housed 20.1675g, five methyl diethylentriamine 3.2494g, stannous octoate 7.596g, methyl-phenoxide 78g, mechanical stirring Homogeneous phase mixing, the oxygen in bubbling 5min eliminating system, continues blistering reaction 3.5h in the oil bath pan of 110 DEG C, and transformation efficiency is 90%.Molecular weight Mn=7100 is recorded, molecular weight distribution PDI=1.23 with gel permeation chromatography GPC.This reacting middle catalyst consumption is the 500ppm of monomer molar amount, obtains molecular weight controlled, the polymkeric substance that molecular weight distribution is narrower.
(2) preparation of the polyurethane grafted polystyrene water dispersion of polystyrene/urethane=6.67% (mass ratio)
First 19g polyether Glycols (N220), 1g polyether-tribasic alcohol (N330), 2.6198g dimethylol propionic acid being added is equipped with in the four-hole boiling flask of stirring rake, is warming up to 120 DEG C and makes it to mix and get rid of small molecules.Then be cooled to 60 DEG C, add 7.95324g tolylene diisocyanate, 8.333g polystyrene solution (2.333g polystyrene, 6gN-methyl-2-pyrrolidone) controls its-NCO/-OH=1.5:1.Be warming up to 80 DEG C of reaction 3h.Cooling after terminating, room temperature adds 15g acetone regulation system viscosity.Add the neutralization of 1.6075g triethylamine, and be scattered in 117g water.Obtain urethane-polystyrene water dispersion that solid content is 20wt%.Wherein N330 and polyether-tribasic alcohol add with the ratio of mol ratio 1:1, make the average functionality of monomer in reaction system be 2.
According to above method, prepare respectively polystyrene consumption account for urethane quality (urethane quality be N220, N330, polystyrene, dimethylol propionic acid, tolylene diisocyanate and triethylamine quality and) be the polyurethane polystyrene interpolymer water dispersion of 0wt%, 13.53wt%, 18.67wt%, 23.05wt%.
The polyurethane grafted polystyrene water dispersion measuring mechanical property of embodiment 1 the results are shown in following table:
The polyurethane polystyrene water dispersion measuring mechanical property of embodiment 2 the results are shown in following table:

Claims (9)

1. a preparation method for polyurethane grafted polystyrene water dispersion, is characterized in that: comprise the following steps:
(1) preparation of terminal hydroxy group polystyrene: initiator, polystyrene, catalyzer, part, reductive agent and solvent I is joined in reaction vessel, reaction system is vacuumized, inflated with nitrogen 5min, 110 DEG C are reacted 0.5 ~ 10 hour, obtained terminal hydroxy group polystyrene, molecular weight distribution ﹤ 2.0;
(2) preparation of polyurethane grafted polystyrene water dispersion: hydrophilic chain extender, dibasic alcohol and trivalent alcohol are added in reaction vessel, is warming up to 100 ~ 150 DEG C, remove small molecules 5 ~ 15min; Then less than 65 DEG C are cooled to, add with the obtained terminal hydroxy group polystyrene of the step (1) of solvent II dissolving and vulcabond, be warming up to 80 ~ 95 DEG C, insulation reaction 2 ~ 5h, be cooled to room temperature, add solvent III adjusting viscosity, be cooled to less than 10 DEG C, add neutralizing agent adjust ph to 6 ~ 7; Finally be added to the water the urethane of above-mentioned preparation-polystyrene performed polymer dispersion 3 ~ 6h, obtains polyurethane grafted polystyrene water dispersion.
2. the preparation method of a kind of polyurethane grafted polystyrene water dispersion according to claim 1, it is characterized in that: in described step (1), initiator is an end group is Br, another end group is organic bromo compound of hydroxyl, and organic bromo compound is alpha-brominated isopropylformic acid hydroxyl ethyl ester or alpha-brominated isopropylformic acid hydroxy butyl ester; Catalyzer is the transition metal halide CuCl of oxidation state 2, CuBr 2, FeCl 3or FeBr 3; Part is the one in five methyl diethylentriamine, hexamethyl three second tetramine, two (dimethyl aminoethyl) ether, bipyridine amine or three-(N, N-dimethyl aminoethyl) amine; Reductive agent is the one in stannous octoate, xitix or glucose; Solvent I is the one in toluene, methyl-phenoxide, DMF, tetrahydrofuran (THF), ethyl acetate or 1-Methyl-2-Pyrrolidone.
3. the preparation method of a kind of polyurethane grafted polystyrene water dispersion according to claim 1, it is characterized in that: polystyrene in described step (1): the mol ratio of initiator is 20:1 ~ 500:1, polystyrene: the mol ratio of catalyzer is 1:0.0005 ~ 1:0.00005, catalyzer: the mol ratio of part is 1:10 ~ 1:30, catalyzer: the mol ratio of reductive agent is 1:10 ~ 1:25, and solvent I consumption is 50% of polystyrene quality.
4. the preparation method of a kind of polyurethane grafted polystyrene water dispersion according to claim 1, it is characterized in that: in described step (2), hydrophilic chain extender is with one or more in the hydrophilic group dibasic alcohol of carboxyl, sulfonic group or tertiary amine groups, hydrophilic chain extender be dimethylol propionic acid, dihydroxyl half ester, dimethylolpropionic acid, N-tri-(methylol) methyl glycine, BDO-2-sodium sulfonate and derivative thereof, in one or more.
5. the preparation method of a kind of polyurethane grafted polystyrene water dispersion according to claim 1, is characterized in that: in described step (2), dibasic alcohol is the one in polyester diol, polyether Glycols, vinylformic acid dibasic alcohol, castor-oil plant oils dibasic alcohol, PCDL or polytetrahydrofuran dibasic alcohol; Trivalent alcohol is the one in polyester trivalent alcohol, polyether-tribasic alcohol, vinylformic acid trivalent alcohol, castor-oil plant oils trivalent alcohol, polycarbonate trivalent alcohol or polytetrahydrofuran trivalent alcohol.
6. the preparation method of a kind of polyurethane grafted polystyrene water dispersion according to claim 1, it is characterized in that: in described step (2), vulcabond is diphenylmethanediisocyanate, tolylene diisocyanate, isophorone diisocyanate, naphthalene-1,5-vulcabond, 2, one in 6-vulcabond methyl caproate, 1,6-hexyl diisocyanate.
7. the preparation method of a kind of polyurethane grafted polystyrene water dispersion according to claim 1, it is characterized in that: in described step (2), solvent II is N-Methyl pyrrolidone, phenyl ether, methyl-phenoxide, toluene, dimethylbenzene, N, the one in N-dimethylformamide, pimelinketone, butylacetate, dimethyl sulfoxide (DMSO).Solvent III is the one in acetone, butanone, methylethylketone, dioxane, N, N-dimethylformamide.
8. the preparation method of a kind of polyurethane grafted polystyrene water dispersion according to claim 1, is characterized in that: in described step (2), neutralizing agent is the one in triethylamine, dimethylethanolamine, diethanolamine, methylamine, ammoniacal liquor, sodium hydroxide or potassium hydroxide.
9. the preparation method of a kind of polyurethane grafted polystyrene water dispersion according to claim 1, it is characterized in that: vulcabond in step (2) in described step (2), dibasic alcohol, trivalent alcohol, hydrophilic chain extender, terminal hydroxy group polystyrene, feed intake according to mol ratio NCO/OH=0.6:1 ~ 1.5:1, hydrophilic chain extender quality accounts for vulcabond, dibasic alcohol, trivalent alcohol, hydrophilic chain extender, 4 ~ 8% of terminal hydroxy group polystyrene quality summation, neutralizing agent consumption is 36% ~ 120% of hydrophilic chain extender molar mass, terminal hydroxy group polystyrene and trivalent alcohol mol ratio are 1:1, the solid content of the polyurethane grafted polystyrene water dispersion of preparation is 5 ~ 30wt%.
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