CN104086699B - A kind of non-commixed type high stability polyacrylic ester water swelling rubber and its preparation method - Google Patents
A kind of non-commixed type high stability polyacrylic ester water swelling rubber and its preparation method Download PDFInfo
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Abstract
The present invention provides non-commixed type high stability polyacrylic ester water swelling rubber and its preparation method, the present invention first letex polymerization prepare the multipolymer of acrylate and vinyl cyanide, then product hydrolysis is obtained the multipolymer of acrylate and sodium acrylate, finally by resin drying and be cross-linked, obtain water-swelling ACM rubber. The present invention adopts chemical synthesis to prepare polyacrylic ester (ACM) water swelling rubber, propose and introduce itrile group in the polymerization process of rubber, then hydrolysis obtains carboxylic acid sodium hydrophilic radical, have obviously compared with chemical graft process and physical blending process evenly structure, owing to hydrophilic radical cannot depart from rubber backbone, therefore structural stability is better, hydrophilic radical on the molecular chain of gained water swelling rubber is carboxylic acid sodium, can water-swelling in hot environment, expansion multiplying power height, mechanical strength is good, it is possible to meet the requirement of complicated environment and special occasions.
Description
Technical field
The invention belongs to Polymer Synthesizing and performances areas, it is specifically related to a kind of non-commixed type high stability polyacrylic ester water swelling rubber and its preparation method.
Background technology
Water swelling rubber is the new function material producing dilatational strain after a kind of water suction, rubber matrix is introduced wetting ability functional group make, it has certain water suction and water retention capacity, maintains the snappiness of rubber (continuous phase) and good mechanical property simultaneously.
Water swelling rubber is because having unique water-swelling sealing, with the characteristic of water sealing, being widely used as the on-the-spot fast blockage that material and dam are only leaked in the sealings such as the engineering project deformation seam of the construction works such as subway, tunnel, motorway, construction joint, pipeline connection.
At present, the rubber substrate of water swelling rubber generally selects the rubber that polarity is big, bond properties good, elasticity is big and degree of crystallinity is high, such as chloroprene rubber (CR), styrene-butadiene rubber(SBR) (SBR), paracril (NBR), chlorinated polyethylene rubber (CPE), ethylene-vinyl acetate rubber (EVM) etc. The hydroaropic substance of water swelling rubber mainly contains the synthesizing high-hydroscopicity resins such as base polyurethane prepolymer for use as, polyacrylic, polyacrylamide system, polyethenol series, and modification height sodium bentonite, white carbon black, polyvinyl alcohol etc.
The water-retaining capacity of polyacrylic water-absorbing resin is strong, has excellent water-retentivity, and still has very high intensity under height water suction state, is the more system occurred in water swelling rubber at present. But owing to its structure differs relatively big with rubber, after water suction, water-absorbing resin easily precipitates out from simple co-mixing system, causes water-retaining capacity and rate of expansion decline.
More effectively improving the consistency with rubber by used in combination for the water-absorbing resin of number of different types than being used alone a kind of water-absorbing material, the precipitation reducing water-absorbing resin comes off, and improves water absorbing properties and the mechanical strength of water swelling rubber simultaneously.
The preparation method of current water swelling rubber mainly contains two kinds: physical blending and chemical graft.
Physical blending type water swelling rubber preparation technology is simple, raw material sources are extensive, with low cost, but the strong cohesive force of polarity water-absorbing resin own is big, in rubber, dispersion property is not got well and poor compatibility, after immersion, water-absorbing resin is easily de-from rubber separates out, rate of expansion and tensile strength decline after Reusability, so it is very crucial to improve both consistencies, normally add amphipathic expanding material to improve the consistency of system inside. Such as: polyoxyethylene-b-butyl polyacrylate amphipathic nature block polymer can as the expanding material of natural rubber and sodium polyacrylate, and its tensile strength, elongation at break and water-swelling property are improved.
Chemical graft type water swelling rubber by chemical reaction, hydrophilic radical or segment is grafted to the rubber with water-retaining capacity obtained on rubber macromolecule. Compared with commixed type, owing to hydrophilic radical is incorporated on high polymer main chain with chemical bonded refractory, water swelling rubber micro compatibility and intensity are better. But chemical graft process reaction difficulty, technique is loaded down with trivial details, and cost is higher. The preparation of chemical graft type water swelling rubber is divided into again: in-situ preparation water-absorbing resin carries out grafting and directly adds the method for water-absorbing resin grafting. Such as: can add sodium acrylate monomers in EPDM rubber, fabricated in situ absorption resin of sodium polyacrylate is also grafted on EPDM; Can also directly add in polyacrylic resin to EPDM and carry out graft reaction.
At present, it is that physical blending or chemical graft type water swelling rubber all exist two-phase poor compatibility, or do not have chemical bond to connect, or only a small amount of chemical bond connects, and there is internal structure less stable, after life-time service, water-absorbing resin precipitates out, the problem of expansion rate of water absorption decline, due to the stress relaxation under compressing for a long time, water-absorbing resin precipitates out, and expansion rate of water absorption reduces greatly. Owing to water swelling rubber weather resistance is not good, adapt to face wideless, the requirement under some particular surroundingss cannot be met.
It is known that, after Water Swelling Rubber Made by Blending water suction, quality turnover rate is higher than graft type, but the quality turnover rate of graft type water swelling rubber is also higher, such as: water swelling rubber quality turnover rate prepared by sodium acrylate situ-formed graft paracril is at 6 ~ 15wt%, therefore, these water swelling rubbers are difficult to repeatedly absorb water, and once after water suction, performance will rapid decrease.
Summary of the invention
For the above-mentioned defect existed in prior art, the present invention provides a kind of non-commixed type high stability polyacrylic ester water swelling rubber and its preparation method, the present invention first letex polymerization prepare the multipolymer of acrylate and vinyl cyanide, then product hydrolysis is obtained the multipolymer of acrylate and sodium acrylate, finally by resin drying and be cross-linked, obtain water-swelling ACM rubber.
It is an object of the invention to: (1) has the polyacrylic ester water swelling rubber (i.e. ACM rubber) of water-swelling ability with chemical synthesis preparation, make hydrophilic radical be evenly distributed on molecular chain, obtain the synthesis type water swelling rubber that structure is different from commixed type and graft type. (2) the ACM rubber with chemical synthesis preparation with water-swelling ability, obtains than commixed type and graft type good endurance, it is possible to repeatedly absorb water, and there is not the water swelling rubber that water-absorbing resin precipitates out problem.
For achieving the above object, the present invention is achieved by the following technical solutions:
A preparation method for non-commixed type high stability polyacrylic ester water swelling rubber, it comprises the following steps:
(1) emulsifying agent, ethyl propenoate, vinyl cyanide and water are added in the reactor of drying and obtain emulsion, stir and lead to nitrogen row's oxygen, after being warming up to 60 ~ 90 DEG C, add the initiator accounting for above-mentioned emulsion gross weight 0.2wt%, reaction 4 ~ 11h;
Wherein, described emulsifying agent is the mixture of polyoxyethylene nonylphenol ether and sodium lauryl sulphate, and emulsifying agent consumption is 0.5 ~ 2wt% of described emulsion gross weight; Vinyl cyanide accounts for 2 ~ 20wt% of emulsion gross weight, and ethyl propenoate accounts for 8 ~ 36wt% of emulsion gross weight, and surplus is water;
(2) by the drying of gained emulsion except water, obtain acrylic ester-acrylonitrile copolymer resin, acrylic ester-acrylonitrile copolymer resin is added in aqueous sodium hydroxide solution and is hydrolyzed, hydrolysis temperature 70 ~ 95 DEG C, hydrolysis time 2 ~ 6h; Wherein aqueous sodium hydroxide solution concentration is the mass ratio of 40wt%, resin and aqueous sodium hydroxide solution is 1:2.5, is hydrolyzed complete, takes out product deionized water and is washed till neutrality, obtains copolymer resin;
(3) epoxy crosslinking agent or poly-hydroxy linking agent are added in described copolymer resin, the consumption of described linking agent is 1 ~ 6wt% of copolymer resin, in two roller mill, sheet is rolled under room temperature, then it is transferred on vulcanizer and carries out sulfuration, curing temperature is 120 ~ 160 DEG C, sulfide stress is 5-10MPa, and curing time 30 ~ 90 minutes, obtains polyacrylic ester water swelling rubber.
Further improvement to technique scheme: also containing butyl acrylate, methyl acrylate and ethyl acrylate in described emulsion, wherein butyl acrylate accounts for 0.1 ~ 34wt% of emulsion gross weight, methyl acrylate accounts for 0.1 ~ 16wt% of emulsion gross weight, and ethyl acrylate accounts for 0.1 ~ 8wt% of emulsion gross weight.
Further improvement to technique scheme: in described step (1), the mass ratio of polyoxyethylene nonylphenol ether and sodium lauryl sulphate is 2 ~ 3:1.
Further improvement to technique scheme: in described step (1), initiator is the one in ammonium persulphate, Potassium Persulphate, benzoyl peroxide or isopropyl benzene hydroperoxide-tetraethylene pentamine.
Further improvement to technique scheme: stir 30min, rotating speed 150r/min in described step (1).
Further improvement to technique scheme: in described step (3), epoxy crosslinking agent is one or more in bisphenol A type epoxy resin, trihydroxymethylpropanyltri diglycidyl ether, tetrahydrophthalic acid 2-glycidyl ester, butanediol diglycidyl ether, ethylene glycol diglycidylether or glycerin triglycidyl ether.
Further improvement to technique scheme: in described step (3), poly-hydroxy linking agent is one or more in butyleneglycol, ethylene glycol, hexylene glycol, TriMethylolPropane(TMP), glycerine or tetramethylolmethane.
Present invention also offers the non-commixed type high stability polyacrylic ester water swelling rubber that the preparation method described in utilization obtains.
The water absorbent rate of described water swelling rubber reaches 102-215%, and the front Shao's A hardness that absorbs water is 80-91, Shao A hardness 35-55 after water suction; Tensile strength 13.1 ~ 25.6MPa before water suction, fracture rate elongation 80-409%, water suction back draft intensity is 2.8-3.2MPa, fracture rate elongation 99-245%.
Described water swelling rubber quality turnover rate is 0.2 ~ 0.5wt%, and repeatedly after absorbent drying 10 times, quality turnover rate is only 1 ~ 1.4wt%.
Compared with prior art, advantage and the technique effect of the present invention be: for foregoing invention object, the present invention adopts chemical synthesis to prepare polyacrylic ester (ACM) water swelling rubber, propose in the polymerization process of rubber, indirectly introduce hydrophilic radical, make hydrophilic radical " growth " in rubber backbone, have obviously compared with chemical graft process and physical blending process evenly structure, owing to hydrophilic radical cannot depart from rubber backbone, therefore structural stability is better, can repeated multiple times water-swelling, do not exist water-absorbing resin precipitate out problem. Hydrophilic radical on the molecular chain of gained water swelling rubber is carboxylic acid sodium, it is possible to water-swelling in hot environment, expansion multiplying power height, and mechanical strength is good, it is possible to meet the requirement of complicated environment and special occasions.
Synthesis type ACM water swelling rubber prepared by the present invention has the stability obviously more superior than commixed type and graft type, quality turnover rate is 0.2 ~ 0.5wt%, repeatedly after absorbent drying 10 times, quality turnover rate is only 1.0 ~ 1.4wt%, being significantly less than grafting and Water Swelling Rubber Made by Blending, after repeated multiple times water suction, property retention is substantially constant.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum before and after acrylic ester-acrylonitrile copolymer of the present invention hydrolysis.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Embodiment 1
Described in the present embodiment, the preparation method of non-commixed type high stability polyacrylic ester water swelling rubber comprises the following steps:
1. emulsifying agent 1wt%, ethyl propenoate 32.4wt%, methyl acrylate 3.4wt%, vinyl cyanide 4wt%, butyl acrylate 0.1wt%, ethyl acrylate 0.1wt%, water 59wt% are added in dry reactor and obtain emulsion, stir and lead to nitrogen 30min, rotating speed 150r/min, after being warming up to 60 DEG C, adding and account for above-mentioned emulsion total mass 0.2wt% ammonium persulfate initiator, reaction 11h terminates.
Wherein, emulsifying agent is polyoxyethylene nonylphenol ether (OP-10) and sodium lauryl sulphate (SDS) mixture, and the mass ratio of OP-10 and SDS is 2:1.
From the infrared spectrum (Fig. 1) before and after acrylic ester-acrylonitrile copolymer hydrolysis it may be seen that be hydrolyzed rear 2250cm-1Place's C �� N absorption peak disappears, and illustrates that vinyl cyanide is substantially all converted into sodium acrylate in hydrolytic process, and major part acrylate is not hydrolyzed. With the molecular weight before and after gel permeation chromatography (GPC) test hydrolysis, before hydrolysis, weight-average molecular weight is 12.9 �� 105, it is 10.5 ~ 11.2 �� 10 after hydrolysis5, still there is higher molecular weight, MW/MnBeing 1.34 before hydrolysis, be 1.41 after hydrolysis, molecular weight distribution slightly becomes wide.
2., by the drying of gained emulsion except water, obtain acrylic ester-acrylonitrile copolymer resin. Acrylic ester-acrylonitrile copolymer resin is added in aqueous sodium hydroxide solution and is hydrolyzed, hydrolysis temperature 90 DEG C, hydrolysis time 5h. Wherein, described aqueous sodium hydroxide solution concentration is the mass ratio of 40wt%, copolymer resin and aqueous sodium hydroxide solution is 1:2.5. It is hydrolyzed complete, takes out product deionized water and be washed till neutral copolymer resin.
With the change of elemental microanalysis method detection hydrolysis after product, it has been found that: C element massfraction reduces by 13.0%, and H element reduces by 4.6%, O element and increases by 8.1%, and N element is reduced to 0%. Ultimate analysis is consistent with infrared result to be shown: major part C �� N disappears after being hydrolyzed, and is converted into carboxylic acid sodium, and the only a small amount of hydrolysis of acrylate.
3. being added by TriMethylolPropane(TMP) in described copolymer resin, the consumption of TriMethylolPropane(TMP) accounts for the 3wt% of copolymer resin, and room temperature rolls sheet in two roller mill. Then being transferred to vulkameter sulfuration, curing temperature is 120 DEG C, and sulfide stress is 5MPa, and curing time 60 minutes obtains ACM water swelling rubber of the present invention.
Performances of water-swelling rubber prepared by the present embodiment is as follows:
Water absorbent rate reaches 102%; The front Shao's A hardness that absorbs water is 83, Shao's A hardness 41 after water suction; Tensile strength 13.1MPa before water suction, fracture rate elongation 81%, water suction back draft intensity is 2.95MPa, fracture rate elongation 230%. Synthesis type ACM water swelling rubber quality turnover rate prepared by the present invention is 0.2wt%, and repeatedly after absorbent drying 10 times, quality turnover rate is only 1.1wt%, is significantly less than grafting and Water Swelling Rubber Made by Blending.
Embodiment 2
Described in the present embodiment, non-commixed type high stability polyacrylic ester water swelling rubber and its preparation method comprise the following steps:
1. emulsifying agent 1wt%, ethyl propenoate 30wt%, butyl acrylate 4.8wt%, vinyl cyanide 5wt%, methyl acrylate 0.1wt%, ethyl acrylate 0.1wt%, water 59wt% are added in dry reactor and obtain emulsion, logical nitrogen also stirs 30min, rotating speed 150r/min, after being warming up to 60 DEG C, adding 0.2wt% ammonium persulfate initiator, reaction 11h terminates.
Wherein, emulsifying agent is polyoxyethylene nonylphenol ether (OP-10) and sodium lauryl sulphate (SDS) mixture, and the mass ratio of OP-10 and SDS is 2.5:1.
2., by the drying of gained emulsion except water, obtain acrylic ester-acrylonitrile copolymer resin. Acrylic ester-acrylonitrile copolymer resin is added in aqueous sodium hydroxide solution and is hydrolyzed, hydrolysis temperature 95 DEG C, hydrolysis time 6h. Wherein, described aqueous sodium hydroxide solution concentration is the mass ratio of 40wt%, copolymer resin and aqueous sodium hydroxide solution is 1:2.5. It is hydrolyzed complete, takes out product deionized water and be washed till neutrality.
3. being added by trihydroxymethylpropanyltri diglycidyl ether in the copolymer resin after hydrolysis, the consumption of trihydroxymethylpropanyltri diglycidyl ether accounts for the 5wt% of copolymer resin, and room temperature rolls sheet in two roller mill. Then being transferred to vulkameter sulfuration, curing temperature is 130 DEG C, and sulfide stress is 5MPa, and curing time 60 minutes, obtains ACM water swelling rubber.
Performances of water-swelling rubber prepared by the present embodiment is as follows:
Water absorbent rate reaches 151%, and the front Shao's A hardness that absorbs water is 80, Shao's A hardness 35 after water suction; Tensile strength 14.2MPa before water suction, fracture rate elongation 112%, water suction back draft intensity is 2.8MPa, fracture rate elongation 245%. Synthesis type ACM water swelling rubber quality turnover rate prepared by the present invention is 0.3wt%, and repeatedly after absorbent drying 10 times, quality turnover rate is only 1.3wt%, is significantly less than grafting and Water Swelling Rubber Made by Blending.
Embodiment 3
A kind of non-commixed type high stability polyacrylic ester water swelling rubber and its preparation method
1. emulsifying agent 1wt%, ethyl propenoate 30wt%, methyl acrylate 1.8wt%, vinyl cyanide 8wt%, butyl acrylate 0.1wt%, ethyl acrylate 0.1wt% and water 59wt% are added in dry reactor and obtain emulsion, logical nitrogen also stirs 30min, rotating speed 150r/min, after being warming up to 60 DEG C, adding 0.2wt% Potassium Persulphate initiator, reaction 6h terminates.
Wherein, emulsifying agent is polyoxyethylene nonylphenol ether (OP-10) and sodium lauryl sulphate (SDS) mixture, and the mass ratio of OP-10 and SDS is 2.5:1.
2., by the drying of gained emulsion except water, obtain acrylic ester-acrylonitrile copolymer resin. Acrylic ester-acrylonitrile copolymer resin is added in aqueous sodium hydroxide solution and is hydrolyzed, hydrolysis temperature 95 DEG C, hydrolysis time 2h. Wherein, aqueous sodium hydroxide solution concentration is the mass ratio of 40wt%, copolymer resin and aqueous sodium hydroxide solution is 1:2.5. It is hydrolyzed complete, takes out product deionized water and be washed till neutrality.
3. being added by glycerine in the copolymer resin after hydrolysis, glycerine consumption is 6wt%, and room temperature rolls sheet in two roller mill. Then being transferred to vulkameter sulfuration, curing temperature is 130 DEG C, and sulfide stress is 6MPa, and curing time 90 minutes, obtains ACM water swelling rubber.
Performances of water-swelling rubber prepared by the present embodiment is as follows:
Water absorbent rate reaches 215%; The front Shao's A hardness that absorbs water is 91, Shao's A hardness 55 after water suction; Tensile strength 25.6MPa before water suction, fracture rate elongation 409%, water suction back draft intensity is 2.77MPa, fracture rate elongation 99%. Synthesis type ACM water swelling rubber quality turnover rate prepared by the present invention is 0.5wt%, and repeatedly after absorbent drying 10 times, quality turnover rate is only 1.4wt%, is significantly less than grafting and Water Swelling Rubber Made by Blending.
Embodiment 4
A kind of non-commixed type high stability polyacrylic ester water swelling rubber and its preparation method
1. emulsifying agent 2wt%, ethyl propenoate 25wt%, methyl acrylate 2wt%, butyl acrylate 0.1wt%, ethyl acrylate 3.9wt%, vinyl cyanide 8wt%, water 59wt% are added in dry reactor, logical nitrogen also stirs 30min, rotating speed 150r/min, after being warming up to 75 DEG C, adding 0.2wt% benzoyl peroxide initiator, reaction 10h terminates.
Wherein, emulsifying agent is polyoxyethylene nonylphenol ether (OP-10) and sodium lauryl sulphate (SDS) mixture, and the mass ratio of OP-10 and SDS is 3:1.
2., by the drying of gained emulsion except water, obtain acrylic ester-acrylonitrile copolymer resin. Acrylic ester-acrylonitrile copolymer resin is added in aqueous sodium hydroxide solution and is hydrolyzed, hydrolysis temperature 85 DEG C, hydrolysis time 6h. Wherein, aqueous sodium hydroxide solution concentration is the mass ratio of 40wt%, copolymer resin and aqueous sodium hydroxide solution is 1:2.5. It is hydrolyzed complete, takes out product deionized water and be washed till neutrality.
3. glycerine and ethylene glycol being added in the copolymer resin after hydrolysis, glycerine consumption is 1wt%, and ethylene glycol consumption is 5%, and room temperature rolls sheet in two roller mill. Then being transferred to vulkameter sulfuration, curing temperature is 130 DEG C, and sulfide stress is 6MPa, and curing time 90 minutes, obtains ACM water swelling rubber.
Performances of water-swelling rubber prepared by the present embodiment is as follows:
Water absorbent rate reaches 193%; The front Shao's A hardness that absorbs water is 90, Shao's A hardness 45 after water suction; Tensile strength 20.4MPa before water suction, fracture rate elongation 277%, water suction back draft intensity is 2.91MPa, fracture rate elongation 139%. Synthesis type ACM water swelling rubber quality turnover rate prepared by the present invention is 0.4wt%, and repeatedly after absorbent drying 10 times, quality turnover rate is only 1.2wt%, is significantly less than grafting and Water Swelling Rubber Made by Blending.
Performances of water-swelling rubber prepared by the present invention is as follows: water absorbent rate reaches 102-215%; The front Shao's A hardness that absorbs water is 80-91, Shao A hardness 35-55 after water suction; Tensile strength 13.1 ~ 25.6MPa before water suction, fracture rate elongation 80-409%, water suction back draft intensity is 2.8-3.2MPa, fracture rate elongation 99-245%. Synthesis type ACM water swelling rubber quality turnover rate prepared by the present invention is 0.2 ~ 0.5wt%, and repeatedly after absorbent drying 10 times, quality turnover rate is only 1 ~ 1.4wt%, is significantly less than grafting and Water Swelling Rubber Made by Blending.
The even copolymerization of sodium acrylate hydrophilic monomer is in polyacrylic rubber molecular backbone chain, it is possible to repeated multiple times water-swelling, there is not the problem that water-absorbing resin precipitates out. It thus is seen that synthesis type ACM water swelling rubber prepared by the present invention has the stability obviously more superior than commixed type and graft type, it is possible to repeated multiple times water suction, property retention is substantially constant.
Above embodiment is only in order to illustrate the technical scheme of the present invention, but not is limited; Although with reference to previous embodiment to invention has been detailed description, for the person of ordinary skill of the art, still the technical scheme described in previous embodiment can being modified, or wherein part technology feature is carried out equivalent replacement; And these amendments or replacement, the spirit and scope of the technical scheme not making essence disengaging the present invention of appropriate technical solution claimed.
Claims (9)
1. the preparation method of a non-commixed type high stability polyacrylic ester water swelling rubber, it is characterised in that it comprises the following steps:
(1) emulsifying agent, ethyl propenoate, vinyl cyanide, butyl acrylate, methyl acrylate, ethyl acrylate and water are added in the reactor of drying and obtain emulsion, stir and lead to nitrogen row's oxygen, after being warming up to 60 ~ 90 DEG C, add the initiator accounting for above-mentioned emulsion gross weight 0.2wt%, reaction 4 ~ 11h;
Wherein, described emulsifying agent is the mixture of polyoxyethylene nonylphenol ether and sodium lauryl sulphate, and emulsifying agent consumption is 0.5 ~ 2wt% of described emulsion gross weight;Vinyl cyanide accounts for 2 ~ 20wt% of emulsion gross weight, and ethyl propenoate accounts for 8 ~ 36wt% of emulsion gross weight; Butyl acrylate accounts for 0.1 ~ 34wt% of emulsion gross weight, and methyl acrylate accounts for 0.1 ~ 16wt% of emulsion gross weight, and ethyl acrylate accounts for 0.1 ~ 8wt% of emulsion gross weight, and surplus is water;
(2) by the drying of gained emulsion except water, obtain acrylic ester-acrylonitrile copolymer resin, acrylic ester-acrylonitrile copolymer resin is added in aqueous sodium hydroxide solution and is hydrolyzed, hydrolysis temperature 70 ~ 95 DEG C, hydrolysis time 2 ~ 6h; Wherein aqueous sodium hydroxide solution concentration is the mass ratio of 40wt%, resin and aqueous sodium hydroxide solution is 1:2.5, is hydrolyzed complete, takes out product deionized water and is washed till neutrality, obtains copolymer resin;
(3) epoxy crosslinking agent or poly-hydroxy linking agent are added in described copolymer resin, the consumption of described linking agent is 1 ~ 6wt% of copolymer resin, in two roller mill, sheet is rolled under room temperature, then it is transferred on vulcanizer and carries out sulfuration, curing temperature is 120 ~ 160 DEG C, sulfide stress is 5-10MPa, and curing time 30 ~ 90 minutes, obtains polyacrylic ester water swelling rubber.
2. the preparation method of non-commixed type high stability polyacrylic ester water swelling rubber according to claim 1, it is characterised in that: in described step (1), the mass ratio of polyoxyethylene nonylphenol ether and sodium lauryl sulphate is 2 ~ 3:1.
3. the preparation method of non-commixed type high stability polyacrylic ester water swelling rubber according to claim 1, it is characterised in that: in described step (1), initiator is the one in ammonium persulphate, Potassium Persulphate, benzoyl peroxide or isopropyl benzene hydroperoxide-tetraethylene pentamine.
4. the preparation method of non-commixed type high stability polyacrylic ester water swelling rubber according to claim 1, it is characterised in that: described step (1) stirs 30min, rotating speed 150r/min.
5. the preparation method of non-commixed type high stability polyacrylic ester water swelling rubber according to claim 1, it is characterised in that: in described step (3), epoxy crosslinking agent is one or more in bisphenol A type epoxy resin, trihydroxymethylpropanyltri diglycidyl ether, tetrahydrophthalic acid 2-glycidyl ester, butanediol diglycidyl ether, ethylene glycol diglycidylether or glycerin triglycidyl ether.
6. the preparation method of non-commixed type high stability polyacrylic ester water swelling rubber according to claim 1, it is characterised in that: in described step (3), poly-hydroxy linking agent is one or more in butyleneglycol, ethylene glycol, hexylene glycol, TriMethylolPropane(TMP), glycerine or tetramethylolmethane.
7. the non-commixed type high stability polyacrylic ester water swelling rubber that preparation method according to the arbitrary item of claim 1-6 obtains.
8. non-commixed type high stability polyacrylic ester water swelling rubber according to claim 7, it is characterised in that: the water absorbent rate of described water swelling rubber reaches 102-215%, and the front Shao's A hardness that absorbs water is 80-91, Shao A hardness 35-55 after water suction; Tensile strength 13.1 ~ 25.6MPa before water suction, fracture rate elongation 80-409%, water suction back draft intensity is 2.8-3.2MPa, fracture rate elongation 99-245%.
9. non-commixed type high stability polyacrylic ester water swelling rubber according to claim 7, it is characterised in that: described water swelling rubber quality turnover rate is 0.2 ~ 0.5wt%, and repeatedly after absorbent drying 10 times, quality turnover rate is only 1 ~ 1.4wt%.
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Application publication date: 20141008 Assignee: Qingdao fortune macromolecule Technology Co., Ltd. Assignor: Qingdao University of Science & Technology Contract record no.: 2017990000346 Denomination of invention: Non-blending type high-stability polyacrylate water absorption swelling rubber and preparation method thereof Granted publication date: 20160608 License type: Exclusive License Record date: 20170904 |
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