CN105064036A - Preparation method and application of hyperbranched polyurethane acrylate interpenetrating polymer network waterproof agent - Google Patents
Preparation method and application of hyperbranched polyurethane acrylate interpenetrating polymer network waterproof agent Download PDFInfo
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Abstract
The invention provides a preparation method of a hyperbranched polyurethane acrylate interpenetrating polymer network waterproof agent. The method comprises the following steps: (1), synthetizing a waterborne polyurethane prepolymer with ends partially capped; (2), introducing hydroxyl-terminated hyperbranched polyester, and grafting by virtue of reaction between isocyanate in the waterborne polyurethane prepolymer and the hydroxyl of the hyperbranched polyester, thereby obtaining a hyperbranched waterborne polyurethane prepolymer; (3), adding part of ethenyl monomers and a neutralizing agent, salifying, and adding deionized water while stirring at a high speed so as to realize dispersion, thereby obtaining a hyperbranched waterborne polyurethane emulsion; and (4), dropwise adding residual ethenyl monomers and an initiator into the hyperbranched waterborne polyurethane emulsion, thereby obtaining a hyperbranched waterborne polyurethane/acrylate interpenetrating network structure emulsion. The emulsion has excellent waterproof performance, good washable and abrasion-resistant performances and does not contain PFOA and PFOS. The hyperbranched structure has a self-recovery function, is capable of realizing self repairing of damaged regions and is long in waterproof performance duration time.
Description
Technical field
The invention belongs to textile printing and dyeing processing and Final finishing field, be specifically related to the preparation method of a kind of super branched polyurethane/polyacrylate interpenetrating network structurally waterproof agent and fabric, the application process of application waterproofing agent.
Background technology
Along with the raising of people's living standard, also more and more higher to the requirement of properties of textile.Without the weaving face fabric of WATER REPELLENT TREATMENT after water suction absorbing sweat, water, sweat penetrate into fabric back and affect appearance of fabrics and comfortableness, limit its application in special climate, the particular surroundings such as daily life and rainy day, hot summer days, high temperature, field.
The block polymer that polyurethane is made up of soft section and hard section, itself have a large amount of hydrogen bonds, micro phase separation structure to a certain degree, polyurethane material has more application in textile auxiliary field.The features such as dissaving polymer has highly branched structure, and viscosity is low, good fluidity, the good easy film forming of dissolubility, and easily carry out terminal groups modification containing a large amount of active function groups, therefore can realize and the programmable compatibility of linear molecule.Super branched polyurethane is except having the common feature of general dissaving polymer, as low in viscosity, solvability strengthens, filming performance well outside, also there are good resistance to water, heat endurance etc., its synthesis technique is simple in addition, cost is low, be conducive to large-scale production, so super branched polyurethane becomes the focus of research gradually on Theory and applications.
Both advantages can combine by acrylic acid modified polyurethane, the method of its modification has physical blending process, crosslinked blending method, interpenetrating polymer networks (IPN), copolymerization method, wherein IPN technology nearly two is rapidly developed during the last ten years and applies, due to mutually running through between interpenetrating networks, tangle and produce to force and dissolve each other and cooperative effect, making IPN material have the feature that is separated on not phase-splitting macroscopically and microcosmic, is the effective ways preparing high performance water proof agent.Research in recent years about polyurethane/polyacrylate latex interpenetrating networks IPN is existing many, but have not been reported about the preparation of super branched polyurethane/polyacrylate IPN waterproofing agent.
Traditional waterproofing agent is based on Organic fluoride, mainly 8-C long-chain perfluoroalkyl product, and these waterproofing agents all contain PFOS based compound (PFOS) and perfluoro caprylic acid amine (PFOA), PFOA, PFOS are moderately toxic liver carcinogenic substances, the cancered risk of the mankind can be increased, there is embryotoxicity and potential neurotoxicity in addition; Do not decompose in the environment with in organism, bioconcentration is strong, can cause organism fat metabolic disturbance, energy metabolism impairment, induction peroxidation etc.
In the last few years, many producers had stopped the product producing long fluorine chain.From current substitute, the waterproofing agent of novel 6-C fluorine-containing surfactant raw material manufacture is best substitute products, but it still also exists the problem such as economy and allomeric function.
The method for sorting of current waterproofing agent, major part all utilizes finishing agent to dip textiles, and the textiles washability after the method arranges is poor, and the water resistance duration of textiles is shorter.
Therefore, exploitation one is just needed effectively can to reduce surface energy and don't introduce PFOS, environmentally safe, substitute to health safety non-toxic harmless to ecology, and good water-proof effect, the product that waterproof effect persistence is good.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, preparation method and the application of a kind of super branched polyurethane/polyacrylate interpenetrating network structurally waterproof agent are provided, this waterproofing agent is made to have excellent waterproof effect, washability is good, ABRASION RESISTANCE is good, and not containing PFOS, dissaving structure has from fully recovering function, impaired region can be made to carry out selfreparing, make the waterproofing agent performance duration long.
To achieve these goals, the present invention adopts following technical scheme:
Hyperbranched aqueous polyurethane/polyacrylate passes a preparation method for network structure waterproofing agent mutually, comprises the steps:
(1) preparation of Waterborne Polyurethane Prepolymer: oligomer dihydroxylic alcohols carries out dehydration preliminary treatment under vacuum heating conditions, then by itself and vulcabond prepolymerization reaction 0.5 ~ 5 hour under 55 DEG C ~ 95 DEG C catalyst actions, add hydrophilic chain extender, reaction 0.5 ~ 1 hour is continued at 40 DEG C ~ 60 DEG C, the NCO/OH of this system final is 1.1 ~ 2, then add end-capping reagent, 50 DEG C ~ 80 DEG C reactions 0.5 ~ 3 hour, obtain Waterborne Polyurethane Prepolymer;
(2) preparation of hyperbranched aqueous polyurethane performed polymer: add hyper-branched polyester in Waterborne Polyurethane Prepolymer prepared by step (1), the ratio of NCO/OH controls at 1:1-1:4,55 DEG C ~ 95 DEG C reactions 0.5 ~ 5 hour, obtain hyperbranched aqueous polyurethane performed polymer;
(3) add the acrylic monomers of 1/4 in the hyperbranched aqueous polyurethane performed polymer prepared in step (2), and add neutralizer, add water under high velocity agitation and carry out emulsion dispersion, obtain hyperbranched aqueous polyurethane emulsion;
(4) preparation of hyperbranched aqueous polyurethane/polyacrylate interpenetrating network structure emulsion: under inert gas shielding, the emulsion that step (3) obtains is warming up to 65 ~ 80 DEG C; drip the acrylic monomers of initator, surplus; insulation reaction 2-6 hour, obtains hyperbranched aqueous polyurethane/polyacrylate interpenetrating network structure emulsion that solid content is 20 ~ 40%.
Vulcabond in described step (1) is selected from isophorone diisocyanate (IPDI), toluene di-isocyanate(TDI) (TDI), '-diphenylmethane diisocyanate (MDI), 1, one or more in hexamethylene-diisocyanate (HDI), dicyclohexyl methyl hydride diisocyanate (HMDI).
Oligomer dihydroxylic alcohols in described step (1) is the mixture of one or more in polytetrahydrofuran diol (PTMEG), polyoxypropyleneglycol (PPO), polyethylene glycol (PEG), poly-epsilon-caprolactone glycol (PCL), polyethylene glycol adipate glycol (PEA), poly-adipate glycol-propylene glycol ester glycol (PEPA), polybutylene glyool adipate (PBA), poly-carbonic acid hexylene glycol esterdiol (PCDL).
Hydrophilic chain extender in described step (1) is one or more mixtures in N-phenyldiethanol-amine, N butyl diethanol amine, N-propyl group diethanol amine, N-ethyldiethanolamine, N methyldiethanol amine.
End-capping reagent in described step (1) is the one in a kind of and phenol in hydroxyethyl methylacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate or n-methylolacrylamide, diacetylmonoxime, acetoxime, and end-capping reagent accounts for 30% ~ 50% of NCO amount of substance in synthesizing linear base polyurethane prepolymer for use as.
Hyper-branched polyester in described step (2) is the one in BoltornH20, BoltornH30, BoltornH40.
The neutralizer of described step (3) is the one in formic acid, acetic acid, hydrochloric acid, epoxychloropropane, and its consumption is 90% ~ 150% of hydrophilic chain extender.
In vinyl monomer in described step (3), hard monomer is the one in styrene, methyl methacrylate, acrylonitrile; Soft monomer is the one in butyl acrylate, ethyl acrylate, acrylic acid ethylhexyl, butyl methacrylate; Specific function monomer is the one in dodecafluoroheptyl methacrylate, Hexafluorobutyl mathacrylate, trifluoroethyl methacrylate.
Initator in described step (3) is the one in ammonium persulfate, potassium peroxydisulfate, azodiisobutyronitrile (AIBN), benzoyl peroxide.
The present invention also provides a kind of fabric applying the hyperbranched aqueous polyurethane/polyacrylate interpenetrating network structurally waterproof agent of above-mentioned preparation method's gained.
The technique for applying method of above-mentioned fabrics is as follows: dressing liquid concentration: be not less than 20g/L; Technique: → 100 DEG C of oven dry → 170 DEG C × 120s HEAT SETTING is rolled in a leaching one, and wherein, the liquid carrying rate that step is rolled in a leaching one is 80-100%.
The invention has the beneficial effects as follows:
1, to have viscosity low for super branched polyurethane, good film-forming property, and cost is low, and raw material such as to be easy to get at the feature, and therefore during preparation, technique is simple, convenient operation, and dissaving structure has from fully recovering function, and impaired region can be made to carry out selfreparing.
2, inierpeneirating network structure is formed after hyperbranched polyurethane, polymerization of vinyl monomer, due to mutually running through between interpenetrating networks, tangle and produce to force and dissolve each other and cooperative effect, there is the feature that is separated on not phase-splitting macroscopically and microcosmic, and containing low-surface-energy fluorine material, there is excellent water resistance.
3, the reactive isocyanate groups containing end-blocking, can obtain reactivity by deblocking at a certain temperature again, can have the combination of chemical bond, provide excellent washing fastness with fiber.
Detailed description of the invention
Below by specific embodiment, the present invention is further illustrated, but protection content of the present invention is not limited to following examples.
embodiment 1
(1) preparation of Waterborne Polyurethane Prepolymer: take 100 grams of polyoxypropyleneglycol N210 in four-hole boiling flask, and be heated to 110 DEG C, 100min is processed under the vacuum of-0.098MPa, add 44.46 grams of IPDI, 70 DEG C of reactions 4 hours, reaction system is cooled between 40 DEG C ~ 50 DEG C, 8.93 grams of N methyldiethanol amines are evenly dripped with dropping funel in 30min, keep reaction temperature at 40 DEG C ~ 50 DEG C, reaction 30min, add the end capping reaction that 1.3 grams of hydroxyethyl methylacrylates and 1.04 grams of phenol carry out part, 60 DEG C of reactions 1.5 hours, obtain Waterborne Polyurethane Prepolymer,
(2) preparation of hyperbranched aqueous polyurethane performed polymer: add 3.27 grams of hyper-branched polyester BoltornH20 in base polyurethane prepolymer for use as prepared by above-mentioned steps (1), 75 DEG C are reacted 2 hours, obtain hyperbranched aqueous polyurethane performed polymer;
(3) preparation of hyperbranched aqueous polyurethane emulsion: add 4.95 grams of neutralizer glacial acetic acids in the hyperbranched aqueous polyurethane performed polymer obtained in step (2), and add vinyl monomer, 4.6 grams of methyl methacrylates, 4.6 grams of butyl acrylates, 2.3 grams of dodecafluoroheptyl methacrylates, add 797 grams of deionized waters, high-speed stirred is disperseed, and obtains hyperbranched aqueous polyurethane emulsion;
(4) preparation of hyperbranched aqueous polyurethane acrylic acid inierpeneirating network structure emulsion: under nitrogen protection dispersion liquid is warming up to 65 DEG C; add 13.8 grams of methyl methacrylates, 13.8 grams of butyl acrylates, 6.9 grams of dodecafluoroheptyl methacrylates, 0.46 gram of azodiisobutyronitrile (AIBN); insulation reaction 4 hours, obtains hyperbranched aqueous polyurethane/polyacrylate interpenetrating network structure emulsion after being down to room temperature.
embodiment 2
(1) preparation of Waterborne Polyurethane Prepolymer: taking 200 gram-molecular weights is that 2000 polybutylene glyool adipates (PBA) are in four-hole boiling flask, and be heated to 110 DEG C, 100min is processed under the vacuum of-0.098MPa, add 33.64 grams of HDI, 55 DEG C of reactions 5 hours, reaction system is cooled between 40 DEG C ~ 50 DEG C, 12.09 grams of N butyl diethanol amines are evenly dripped with dropping funel in 30min, keep reaction temperature at 40 DEG C ~ 50 DEG C, reaction 30min, add the end capping reaction that 1.01 grams of n-methylolacrylamide and 0.73 gram of acetoxime carry out part, 60 DEG C of reactions 1.5 hours, obtain Waterborne Polyurethane Prepolymer,
(2) preparation of hyperbranched aqueous polyurethane performed polymer: add 3.43 grams of hyper-branched polyester BoltornH30 in base polyurethane prepolymer for use as prepared by above-mentioned steps (1), 75 DEG C are reacted 2 hours, obtain hyperbranched aqueous polyurethane performed polymer;
(3) preparation of hyperbranched aqueous polyurethane emulsion: add 3.8 grams of neutralizer formic acid in the hyperbranched aqueous polyurethane performed polymer obtained in step (2), and add vinyl monomer, 4 grams of methyl methacrylates, 16 grams of butyl acrylates, 4 grams of dodecafluoroheptyl methacrylates, add 488 grams of deionized waters, high-speed stirred is disperseed, and obtains hyperbranched aqueous polyurethane emulsion;
(4) preparation of hyperbranched aqueous polyurethane acrylic acid inierpeneirating network structure emulsion: under nitrogen protection dispersion liquid is warming up to 70 DEG C; add 12 grams of styrene, 36 grams of ethyl acrylates, 12 grams of Hexafluorobutyl mathacrylates, 0.8 gram of potassium peroxydisulfate; insulation reaction 4 hours, obtains hyperbranched aqueous polyurethane/polyacrylate interpenetrating network structure emulsion after being down to room temperature.
embodiment 3
(1) preparation of Waterborne Polyurethane Prepolymer: taking 100 gram-molecular weights is that 1000 polytetrahydrofuran diols (PTMEG) are in four-hole boiling flask, and be heated to 110 DEG C, 100min is processed under the vacuum of-0.098MPa, add 31.32 grams of TDI, 60 DEG C of reactions 2.5 hours, reaction system is cooled between 40 DEG C ~ 50 DEG C, 5.95 grams of N methyldiethanol amines are evenly dripped with dropping funel in 30min, keep reaction temperature at 40 DEG C ~ 50 DEG C, reaction 30min, add the end capping reaction that 2.16 grams of hydroxy propyl methacrylates and 1.3 grams of diacetylmonoximes carry out part, 50 DEG C of reactions 3 hours, obtain Waterborne Polyurethane Prepolymer,
(2) preparation of hyperbranched aqueous polyurethane performed polymer: add 3.37 grams of hyper-branched polyester BoltornH40 in base polyurethane prepolymer for use as prepared by above-mentioned steps (1), 95 DEG C are reacted 0.5 hour, obtain hyperbranched aqueous polyurethane performed polymer;
(3) preparation of hyperbranched aqueous polyurethane emulsion: add 4.5 grams of neutralizer glacial acetic acids in the hyperbranched aqueous polyurethane performed polymer obtained in step (2), and add vinyl monomer, 4.5 grams of methyl methacrylates, 6 grams of butyl acrylates, 4.5 grams of trifluoroethyl methacrylates, add 460 grams of deionized waters, high-speed stirred is disperseed, and obtains hyperbranched aqueous polyurethane emulsion;
(4) preparation of hyperbranched aqueous polyurethane acrylic acid inierpeneirating network structure emulsion: under nitrogen protection dispersion liquid is warming up to 65 DEG C; add 13.5 grams of methyl methacrylates, 18 grams of butyl methacrylates, 13.5 grams of dodecafluoroheptyl methacrylates, 0.6 gram of AIBN; insulation reaction 4 hours, obtains hyperbranched aqueous polyurethane/polyacrylate interpenetrating network structure emulsion after being down to room temperature.
In order to verify the waterproof effect of textiles after hyperbranched aqueous polyurethane of the present invention/polyacrylate interpenetrating network structurally waterproof agent process, investigate by standard method.Described standard method adopts AATCC method of testing 22-2010 to investigate waterproof effect.
Washing durability is that the textiles put in order is carried out 10 standard wash, then investigates water resistance.
| Numbering | Waterproof effect | Waterproof effect after standard wash 10 times |
| Embodiment 1 | 100 | 95+ |
| Embodiment 2 | 100 | 95+ |
| Embodiment 3 | 95 | 90+ |
The foregoing is only preferred embodiments of the present invention, in fact each concrete raw material cited by the present invention, and the bound of each raw material, interval value, and the bound of technological parameter (as temperature, time etc.), interval value can realize the present invention, do not enumerate embodiment at this.
Above embodiment is not in order to limit the present invention, and the usual change that those skilled in the art carries out within the scope of technical solution of the present invention and replacement all should be included in protection scope of the present invention.
Claims (10)
1. a preparation method for hyperbranched aqueous polyurethane/acrylic acid inierpeneirating network structure waterproofing agent, comprises the steps:
(1) preparation of Waterborne Polyurethane Prepolymer: oligomer dihydroxylic alcohols carries out dehydration preliminary treatment under vacuum heating conditions, then by itself and vulcabond prepolymerization reaction 0.5 ~ 5 hour under 55 DEG C ~ 95 DEG C catalyst actions, add hydrophilic chain extender, reaction 0.5 ~ 1 hour is continued at 40 DEG C ~ 60 DEG C, the NCO/OH of this system final is 1.1 ~ 2, then add end-capping reagent, 50 DEG C ~ 80 DEG C reactions 0.5 ~ 3 hour, obtain Waterborne Polyurethane Prepolymer;
(2) preparation of hyperbranched aqueous polyurethane performed polymer: add hyper-branched polyester in Waterborne Polyurethane Prepolymer prepared by step (1), the ratio of NCO/OH controls at 1:1-1:4,55 DEG C ~ 95 DEG C reactions 0.5 ~ 5 hour, obtain hyperbranched aqueous polyurethane performed polymer;
(3) add the acrylic monomers of 1/4 in the hyperbranched aqueous polyurethane performed polymer prepared in step (2), and add neutralizer, add deionized water under high velocity agitation and carry out emulsion dispersion, obtain hyperbranched aqueous polyurethane emulsion;
(4) preparation of super branched polyurethane/polyacrylate interpenetrating network structure emulsion: under inert gas shielding, the emulsion that step (3) obtains is warming up to 65-80 DEG C; drip the acrylic monomers of initator, surplus; insulation reaction 2-6 hour, obtains hyperbranched aqueous polyurethane/polyacrylate interpenetrating network structure emulsion that solid content is 20-40%.
2. preparation method according to claim 1, it is characterized in that: the vulcabond described in step (1) is selected from isophorone diisocyanate, toluene di-isocyanate(TDI), '-diphenylmethane diisocyanate, 1, one or more in hexamethylene-diisocyanate, dicyclohexyl methyl hydride diisocyanate.
3. preparation method according to claim 1, is characterized in that: the oligomer dihydroxylic alcohols described in step (1) is the mixture of one or more in polytetrahydrofuran diol, polyoxypropyleneglycol, polyethylene glycol, poly-epsilon-caprolactone glycol, polyethylene glycol adipate glycol, poly-adipate glycol-propylene glycol ester glycol, polybutylene glyool adipate, poly-carbonic acid hexylene glycol esterdiol.
4. preparation method according to claim 1, it is characterized in that: step (1) described hydrophilic chain extender is one or more mixtures in N-phenyldiethanol-amine, N butyl diethanol amine, N-propyl group diethanol amine, N-ethyldiethanolamine, N methyldiethanol amine, the mass percent of hydrophilic chain extender the line is busy property base polyurethane prepolymer for use as is 4.0% ~ 10.0%.
5. preparation method according to claim 1, it is characterized in that: the end-capping reagent described in step (1) is the one in a kind of and phenol in hydroxyethyl methylacrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate or n-methylolacrylamide, diacetylmonoxime, acetoxime, and end-capping reagent accounts for 30% ~ 50% of NCO amount of substance in synthesizing linear base polyurethane prepolymer for use as.
6. preparation method according to claim 1, is characterized in that: the hyper-branched polyester described in step (2) is the one in BoltornH20, BoltornH30, BoltornH40.
7. preparation method according to claim 1, is characterized in that: the neutralizer described in step (3) is the one in formic acid, acetic acid, hydrochloric acid, and its consumption is 90% ~ 150% of hydrophilic chain extender; Initator described in step (3) is the one in ammonium persulfate, potassium peroxydisulfate, azodiisobutyronitrile, benzoyl peroxide.
8. preparation method according to claim 1, is characterized in that: in step (3) described vinyl monomer, hard monomer is the one in styrene, methyl methacrylate, acrylonitrile; Soft monomer is the one in butyl acrylate, ethyl acrylate, acrylic acid ethylhexyl or butyl methacrylate; Specific function monomer is the one in dodecafluoroheptyl methacrylate, Hexafluorobutyl mathacrylate, trifluoroethyl methacrylate.
9. a fabric, is characterized in that: application rights requires 1 to the 8 arbitrary described hyperbranched aqueous polyurethane obtained by preparation method/polyacrylate interpenetrating network structurally waterproof agent.
10. hyperbranched aqueous polyurethane/polyacrylate interpenetrating network structurally waterproof agent technique for applying the method for fabric according to claim 9, is characterized in that: dressing liquid concentration is not less than 20g/L; The technique of application is: → 100 DEG C of oven dry → 170 DEG C × 120s HEAT SETTING is rolled in a leaching one, and wherein, the liquid carrying rate rolling step in a leaching one is 80-100%.
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