CN103360564A - Hyperbranched non-ionic waterborne polyurethane and application thereof in fibreglass sizing agent - Google Patents
Hyperbranched non-ionic waterborne polyurethane and application thereof in fibreglass sizing agent Download PDFInfo
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Abstract
The invention relates to the technical field of hyperbranched polymers, and specially relates to a hyperbranched non-ionic waterborne polyurethane. The hyperbranched non-ionic waterborne polyurethane is prepared by: reacting succinic anhydride with methoxy polyethylene glycol to generate a carboxyl-terminated hydrophilic polymer; adding the hydrophilic polymer into a hydroxyl-terminated hyperbranched polymer, and reacting to obtain a modified hyperbranched polymer; and reacting the modified hyperbranched polymer with a polyether polyol, isocyanate and a silane coupling agent to obtain the hyperbranched non-ionic waterborne polyurethane. The invention also discloses an application of the hyperbranched non-ionic waterborne polyurethane in a fiberglass sizing agent. The hyperbranched non-ionic waterborne polyurethane helps to improve bonding strength between fiberglass and a matrix resin, also possesses very strong bonding strength with the matrix resin, and helps to improve the interface bonding strength; also as a fiberglass film-forming agent, the hyperbranched non-ionic waterborne polyurethane possesses excellent elasticity and wear resistance, and helps fiberglass not to split, to be without filoselle, and to keep integrity of fiberglass chopped strand to the maximum extent during chopping.
Description
Technical field
The present invention relates to the hyperbranched polymer technical field, particularly a kind of hyperbranched non-ionic water polyurethane also relates to the application of described hyperbranched non-ionic water polyurethane in glass fiber infiltration agent.
Background technology
Glass fibre is a kind of strongthener of thermoplastic composite (FTRP), and good heat resistance is arranged, and ageing-resistant performance is good, chemical resistance corrosion, the advantage such as electrical insulation properties is good, and mechanical property is good, and price is low.Glass fibre is added the bending that can improve the FTRP matrix material in the middle of the FTRP material, stretch, shock strength and rigidity, glass fibre strengthens the FTRP material and is widely used in chemical industry, building, traffic, the industries such as electronics.But, not surface treated glass fibre in the FTRP material because self boundling and electrostatic interaction cause dispersed badly, affect composite property.Thereby the surface treatment situation that can say glass fibre directly affects mechanical property and the outward appearance of FRTP.Process now glass fibre mainly usefulness be glass fiber infiltration agent, treating compound mainly plays bonding boundling, lubrication friction such as destatics at the effect.In drawing process, treating compound is directly overlayed on fiberglass surfacing, satisfies the glass fiber wire-drawing processing requirement, also makes glass fibre have secondary workability, has for example improved the dispersiveness of glass fibre, formability, choppability etc.Treating compound has good consistency with the matrix resin that is enhanced, for example reactive behavior and cohesiveness.Glass fibre after being processed by treating compound can directly use in the FRTP moulding process, needn't again process.Glass fiber infiltration agent is usually by membrane-forming agent, coupling agent, lubricant, the compositions such as static inhibitor.Wherein membrane-forming agent is the key ingredient for the treatment of compound, and its consumption in treating compound is maximum.The effect of membrane-forming agent is in wire drawing and winding process glass fiber single filament to be bonded to precursor, plays the stiffness of protective glass fiber and raising glass fibre in the following process process, the performances such as choppability and infusing rate.
Aqueous polyurethane (PU) has the soft or hard section that can regulate, and good springiness intensity greatly can well the protective glass fiber, especially when chopped, can guarantee that glass fibre do not open fibre, and filoselle not keeps the integrity of chopped.Urethane has very strong polarity and most of matrix resin (epoxy simultaneously, polyester) polypropylene (PP) especially, nylon (PA), the thermoplastic materials such as terylene (PET) have very strong adhesive property, mix to use with High Efficient Bonding Agents and can fine solution interface be combined problem.Using aqueous polyurethane to do most of requirement that the glass fibre membrane-forming agent can satisfy chopped strand, is the first-selected membrane-forming agent that chopped strengthens FRTP.
At present, domestic research anion aqueous polyurethane is many, and non-ion aqueous polyurethane is less, but because the particle diameter of anion-type water-thinned polyurethane is less, generally only has 50 ~ 200nm, in the wire drawing coating procedure, easily treating compound is thrown away, reduced the utilization ratio for the treatment of compound, glass fibre static electrification and anion-type water-thinned polyurethane repel, easily cause out fine filoselle, and anion-type water-thinned polyurethane can only use under alkaline condition, define the preparation working conditions for the treatment of compound.In addition, also have a large amount of hydrophilic radicals in the aqueous polyurethane, hydrophilic radical can flock together easily and form hydrophilic microcell during film forming, attracts water molecules, produces swelling, thereby reduces the mechanical property of FTRP.
Summary of the invention
For solve the reduction that exists when above anion aqueous polyurethane is applied to the glass fibre membrane-forming agent utilization ratio for the treatment of compound, easily cause out fine filoselle, define the preparation working conditions for the treatment of compound, easily produce the problem that swelling reduces mechanical property, the present invention has synthesized a kind of hyperbranched non-ionic water polyurethane.
Hyperbranched polymer is similar to branch-shape polymer, and the diameter of Spherical Volume structure is arranged, but also has a large amount of end reactive functional, make it have high-dissolvability, low viscosity, the characteristics such as high reaction activity, separating-purifying is easy in the building-up process, technique is simple, at present at coating, and tackiness agent, auxiliary rheological agents, nano material, biological medicine, the photoelectric material aspect has manifested huge using value.
The present invention also provides the application of above-mentioned hyperbranched non-ionic water polyurethane in glass fiber infiltration agent.
The present invention is achieved by the following measures:
A kind of hyperbranched non-ionic water polyurethane obtains by following steps:
1. Succinic anhydried and poly glycol monomethyl ether reaction are generated the hydrophilic polymer of holding carboxyl,
2. add the hydrophilic polymer of the end carboxyl of step in 1. in the Hyperbranched Polymer with Terminal Hydroxyl, reaction gets the modified ultra-branching polymkeric substance;
3. the modified ultra-branching polymer reaction that 2. polyether glycol, isocyanic ester, silane coupling agent, step is obtained to isocyanate group content is 0%, and aftertreatment gets hyperbranched non-ionic water polyurethane.
Described hyperbranched non-ionic water polyurethane, modified ultra-branching Polymer-supported chain end contain hydroxyl and
, its mol ratio is 1:2～11.
Hydroxyl in the described hyperbranched non-ionic water polyurethane, step (3) in the modified ultra-branching polymkeric substance and the mol ratio of isocyanate group are 1:1 ~ 1.5, and the mol ratio of silane coupling agent and isocyanic ester is 1:1.
Described hyperbranched non-ionic water polyurethane, the core molecule of described Hyperbranched Polymer with Terminal Hydroxyl and AB
2The first-generation terminal hydroxy group polyesteramide that monomer obtains respectively according to 1:3,1:9 or 1:21 molar ratio reaction, s-generation terminal hydroxy group polyesteramide or third generation terminal hydroxy group polyesteramide.
Described hyperbranched non-ionic water polyurethane, step 2. in the mol ratio of hydrophilic polymer of the core molecule of synthetic Hyperbranched Polymer with Terminal Hydroxyl and the step end carboxyl in 1. be 1:1 ~ 22.
Described hyperbranched non-ionic water polyurethane, AB
2Monomer is synthetic according to mol ratio 1:1 by Succinic anhydried and diisopropanolamine (DIPA).
Described hyperbranched non-ionic water polyurethane, used poly glycol monomethyl ether model is mpeg 3 50 ~ 700, isocyanic ester is aliphatic isocyanates IPDI.
The application of described hyperbranched non-ionic water polyurethane in glass fiber infiltration agent.
Described application contains the hyperbranched non-ionic water polyurethane of 8 ~ 12% membrane-forming agent emulsion weight percents in the glass fiber infiltration agent.
Described application also contains 0.2 ~ 0.5wt% lubricant in the glass fiber infiltration agent, 0.1 ~ 0.3wt% static inhibitor, and the PH conditioning agent of 0.1 ~ 0.2wt%, surplus is water.
The below is elaborated with a kind of synthesis step in the hyperbranched non-ionic water polyurethane.
1. an amount of Succinic anhydried is dissolved among the DMAc, adds mpeg 3 50 and catalyzer DMAP in solution, 70 ℃ of reactions 4 hours, generate and contain the hydrophilic polymer of holding carboxyl, reaction equation is as follows:
2. add the hydrophilic polymer of the end carboxyl of step in 1. in the Hyperbranched Polymer with Terminal Hydroxyl, reaction gets the modified ultra-branching polymkeric substance;
The Hyperbranched Polymer with Terminal Hydroxyl preparation process is as follows:
1) an amount of diisopropanolamine (DIPA) is dissolved among the DMAc, pours in the there-necked flask with magnetic stirring apparatus, Succinic anhydried is dissolved among the DMAc, drip in there-necked flask, stirring reaction certain hour under the normal temperature obtains the AB of a carboxyl and two hydroxyls
2The type monomer.Reaction equation is as follows:
2) in above-mentioned system, make the band aqua with toluene, TriMethylolPropane(TMP) is made core molecule, and 140 ℃ of backflows are heated in the Catalyzed by p-Toluenesulfonic Acid agent, minute water, insulation reaction obtains hyperbranched polymer after for some time.Reaction equation is as follows:
3) drip 1. resulting hydrophilic polymer in reaction system, under Catalyzed by p-Toluenesulfonic Acid, under the nitrogen protection, 140 ℃ of lower back flow reaction, minute water continues reaction for some time.Reaction finishes to be cooled to about 110 ℃, and solvent DMAc was removed in underpressure distillation in 1～2 hour, and dripless occurs to the condenser, returns to gradually normal pressure, closes vacuum system and obtains the modified ultra-branching polymkeric substance.Reaction equation is as follows:
3. the modified ultra-branching polymer reaction that 2. polyether glycol, IPDI, silane coupling agent, step is obtained to isocyanate group content is 0%, and aftertreatment gets hyperbranched non-ionic water polyurethane, and concrete operation step is as follows:
1) polyether glycol that measures is added in the reaction vessel of dry cleansing;
2) under the vacuum tightness about-0.090MP, the open cycle water of condensation stirs, and the control temperature is about 90 ℃, and dehydration is cooled to 50 ℃ until substantially anhydrous out the time on the condenser;
3) at N
2Protection is lower, opens stirring, slowly drips IPDI in the complete material of above-mentioned dehydration, strict control temperature of reaction in case the generation of implode reaction dropwises, then slowly is warming up to 80～82 ℃ within half an hour about 50 ℃, keep this temperature range, polymerization under atmospheric pressure reaction 2 hours; Drip a certain amount of silane coupling agent, reaction for some time, survey the modified ultra-branching polymkeric substance that its nco value adds a certain amount of preparation in theoretical scope the time again in the system, improve rotating speed to 3000r/min, viscosity falls with acetone, 80 ℃ of reactions 2 hours, cool to below 40 ℃ amine chain extender hydrazine hydrate and water are diluted according to a certain percentage, in system, slowly drip, in 1 ~ 2h, dropwise, continue to stir 1h, isocyanate group content in the mensuration system, when reaching 0%, chain extension is complete, 50 ℃ of left and right sides underpressure distillation desolventizings, obtain the white emulsion with blue light.
By regulating polyether glycol and isocyanic ester, the synthetic a kind of end of the kind of silane coupling agent and consumption contains-NCO, and the other end contains-Si(OC
2H
5)
3Base polyurethane prepolymer for use as, then with synthetic modified ultra-branching polymer ends-in OH and the base polyurethane prepolymer for use as-the NCO reaction, amount by control modified ultra-branching polymkeric substance can with in the base polyurethane prepolymer for use as-NCO reacts away, and obtains a kind of hyperbranched non-ionic water polyurethane that contains the hydrophilic radical dissaving structure.
Beneficial effect of the present invention:
(1) hyperbranched non-ionic water polyurethane of the present invention has very high degree of crosslinking, improved the water tolerance of aqueous polyurethane, and hyperbranched polymer has lower viscosity, improved the solid content of aqueous polyurethane, the building-up process of this hyperbranched polymer is relatively simple, production cost is lower, is applicable to large-scale industrial production;
(2) hyperbranched non-ionic water polyurethane of the present invention is as the glass fibre membrane-forming agent, avoided the anion-type water-thinned polyurethane particle diameter low and to the shortcoming of the strong dependence of PH, enlarged the use range of glass fibre reinforcement; Simultaneously coupling agent and urethane are combined by the chemical bonding effect, improved the cohesive strength of glass fibre and matrix resin, with matrix resin very strong affinity is arranged also, improved interface bond strength, dissaving structure has improved the degree of crosslinking of aqueous polyurethane, has avoided because the swelling that hydrophilic radical causes reduces the defective of the water tolerance of film;
(3) hyperbranched non-ionic water polyurethane of the present invention also has good elasticity and wear resisting property as the glass fibre membrane-forming agent, can make glass fibre not open fibre when chopped, and filoselle does not at utmost keep glass chopped integrity; Utilize the synthetic treating compound appearance stability of this membrane-forming agent, the convergency stiffness of glass fibre is all had desirable effect, have good future develop.
Embodiment
Below the preparation method of short glass fiber membrane-forming agent of the present invention is described in more detail, its purpose is to illustrate design of the present invention and characteristics, can not limit protection scope of the present invention with this.All equivalences that spirit is done according to the present invention change or modify, and all should be encompassed within protection scope of the present invention.
Example 1
(1) takes by weighing the 0.20mol Succinic anhydried, 0.20mol poly glycol monomethyl ether (350) is dissolved in respectively among an amount of DMAc, then adds there-necked flask, adds 0.5% catalyzer DMAP of reaction monomers total mass in the flask, be warmed up to 70 ℃ of reactions 4 hours, make MPEG-succinate monoester solution;
(2) take by weighing 0.15mol Succinic anhydried, 0.15mol diisopropanolamine (DIPA), at first diisopropanolamine (DIPA) is dissolved among an amount of DMAc, pour into after the dissolving in the there-necked flask with magnetic stirring apparatus, again Succinic anhydried is dissolved with an amount of DMAc, then it slowly is added drop-wise in the there-necked flask, stirs while dripping, approximately drip 0.5 hour, normal-temperature reaction 3 hours obtains AB
2The type monomer.In above-mentioned system, add first 60 mL toluene (toluene is the band aqua), add 0.05mol core molecule TriMethylolPropane(TMP), the 0.5% catalyzer tosic acid that adds the reaction monomers total mass, then begin heating, until boiling, treat to have in the spherical condensation tube to reflux and produce, insulation reaction 7 hours gets Hyperbranched Polymer with Terminal Hydroxyl, slowly drips the MPEG-succinate monoester that step (1) is made in this system, approximately drip 2 hours, the control temperature of reaction is at 90～120 ℃, and reflux water-dividing reacted 4～6 hours, then underpressure distillation desolventizing and excessive (1) product obtain end and contain a small amount of hydroxyl and a large amount of
The modified ultra-branching polymkeric substance of (hereinafter to be referred as R) base;
(3) 0.02mol polyethers 2000 is added in the reaction vessel of dry cleansings, under the vacuum tightness about-0.092MP, open circulating condensing water, open stirring.The control temperature is about 90 ℃, and dehydration is cooled to 50 ℃ until substantially anhydrous out the time on the condenser.At N
2Protection is lower, opens stirring, slowly drips 0.045molIPDI in the complete material of above-mentioned dehydration; strict control temperature of reaction in case the generation of implode reaction dropwises, then slowly is warming up to 80～82 ℃ in 30min about 50 ℃; keep this temperature range, polymerization under atmospheric pressure reaction 2 hours.Then be cooled to 50 ℃, in system, drip the 0.045molKH550 silane coupling agent, be warmed up to 80 ℃ after dropwising and react half an hour, add proper amount of acetone and regulate viscosity, stop to add, after system is down to room temperature, add the modified ultra-branching polymkeric substance 0.015mol that step (2) makes, add 0.5% catalyzer dibutyl tin dilaurate of reaction monomers total mass, be warmed up to 80 ℃, rotating speed is brought up to 3000r/min, reacts 1 hour.Reaction is cooled to room temperature after finishing, the mixing solutions emulsification of adding 0.02mol hydrazine hydrate and 5.56mol water 1 hour.Close N
2Intake valve is opened vacuum system, under the condition about vacuum tightness-0.092MP, and 50 ℃ of lower underpressure distillation desolventizing in 2～3 hours and unreacted monomer.Then close vacuum system, open N
2Intake valve is at N
2Protection is lower, makes system recover normal pressure, is discharged in the plastic containers, obtains hyperbranched non-ionic water polyurethane emulsion.
Soaking the water of joining adding 50wt% in the tank, open stirring, slowly add the hyperbranched non-ionic water polyurethane of the above-mentioned preparation of 10wt% as membrane-forming agent, stir and slowly add successively the 0.4wt% lubricant after 30 minutes, the 0.2wt% static inhibitor, add at last remaining water and use the PH conditioning agent with pH regulator 4～7, obtain treating compound.
The glass fibre reinforced plastic PA66 of processing with this treating compound, wherein the massfraction of glass fibre is 30%, the experiment test interface binding intensity is extracted in utilization, according to standard GB/T1447-2005, measures its tensile strength, elongation at break, according to standard GB/T1449-2005, measure its flexural strength, according to standard GB/T1451-2005, measure its shock strength, the results are shown in Table 1.
Example 2
(1) takes by weighing the 0.60mol Succinic anhydried, 0.60mol poly glycol monomethyl ether (350) is dissolved in respectively among an amount of DMAc, then adds there-necked flask, adds 0.5% catalyzer DMAP of reaction monomers total mass in the flask, be warmed up to 70 ℃ of reactions 4 hours, make MPEG-succinate monoester solution;
(2) take by weighing 0.45mol Succinic anhydried, 0.45mol diisopropanolamine (DIPA), at first diisopropanolamine (DIPA) is dissolved among an amount of DMAc, pour into after the dissolving in the there-necked flask with magnetic stirring apparatus, again Succinic anhydried is dissolved with an amount of DMAc, then it slowly is added drop-wise in the there-necked flask, stirs while dripping, approximately drip 0.5 hour, normal-temperature reaction 3 hours obtains AB
2The type monomer.In above-mentioned system, add first 60 mL toluene (toluene is the band aqua), add 0.05mol core molecule TriMethylolPropane(TMP), the 0.5% catalyzer tosic acid that adds the reaction monomers total mass, then begin heating, until boiling, treat to have in the spherical condensation tube to reflux and produce, insulation reaction got Hyperbranched Polymer with Terminal Hydroxyl in 7 hours, slowly drip the MPEG-succinate monoester that make (1) in this system, approximately drip 2 hours, the control temperature of reaction is at 90～120 ℃, reflux water-dividing, reacted 4～6 hours, then underpressure distillation desolventizing and excessive (1) product obtain the modified ultra-branching polymkeric substance that end contains a small amount of hydroxyl and a large amount of R bases;
(3) 0.02mol polyethers 2000 is added in the reaction vessel of dry cleansings, under the vacuum tightness about-0.092MP, open circulating condensing water, open stirring.The control temperature is about 90 ℃, and dehydration is cooled to 50 ℃ until substantially anhydrous out the time on the condenser.At N
2Protection is lower, opens stirring, slowly drips 0.045molIPDI in the complete material of above-mentioned dehydration; strict control temperature of reaction in case the generation of implode reaction dropwises, then slowly is warming up to 80～82 ℃ in 30min about 50 ℃; keep this temperature range, polymerization under atmospheric pressure reaction 2 hours.Then be cooled to 50 ℃, in system, drip 0.045molKH550, be warmed up to 80 ℃ after dropwising and react half an hour, add proper amount of acetone and regulate viscosity, stop to add, after system is down to room temperature, add the hyperbranched polymer 0.004mol that (2) make, add 0.5% catalyzer dibutyl tin dilaurate of reaction monomers total mass, be warmed up to 80 ℃, rotating speed is brought up to 3000r/min, reacts 1 hour.Reaction is cooled to room temperature after finishing, the mixing solutions emulsification of adding 0.02mol hydrazine hydrate and 5.56mol water 1 hour.Close N
2Intake valve is opened vacuum system, under the condition about vacuum tightness-0.092MP, and 50 ℃ of lower underpressure distillation desolventizing in 2～3 hours and unreacted monomer.Then close vacuum system, open N
2Intake valve is at N
2Protection is lower, makes system recover normal pressure, is discharged in the plastic containers, obtains hyperbranched non-ionic water polyurethane emulsion.
Soaking the water of joining adding 50wt% in the tank, open stirring, slowly add the hyperbranched non-ionic water polyurethane of the above-mentioned preparation of 10wt% as membrane-forming agent, stir and slowly add successively the 0.4wt% lubricant after 30 minutes, the 0.2wt% static inhibitor, add at last remaining water and with the PH conditioning agent PH is regulated 4～7, obtain treating compound.
The glass fibre reinforced plastic PA66 of processing with this treating compound, wherein the massfraction of glass fibre is 30%, the experiment test interface binding intensity is extracted in utilization, according to standard GB/T1447-2005, measures its tensile strength, elongation at break, according to standard GB/T1449-2005, measure its flexural strength, according to standard GB/T1451-2005, measure its shock strength, the results are shown in Table 1.
Example 3
(1) takes by weighing the 0.05mol Succinic anhydried, 0.05mol poly glycol monomethyl ether (350) is dissolved in respectively among an amount of DMAc, then adds there-necked flask, adds 0.5% catalyzer DMAP of reaction monomers total mass in the flask, be warmed up to 70 ℃ of reactions 4 hours, make MPEG-succinate monoester solution;
(2) take by weighing 0.15mol Succinic anhydried, 0.15mol diisopropanolamine (DIPA), at first diisopropanolamine (DIPA) is dissolved among an amount of DMAc, pour into after the dissolving in the there-necked flask with magnetic stirring apparatus, again Succinic anhydried is dissolved with an amount of DMAc, then it slowly is added drop-wise in the there-necked flask, stirs while dripping, approximately drip 0.5 hour, normal-temperature reaction 3 hours obtains AB
2The type monomer.In above-mentioned system, add first 60 mL toluene (toluene is the band aqua), add 0.05mol core molecule TriMethylolPropane(TMP), the 0.5% catalyzer tosic acid that adds the reaction monomers total mass, then begin heating, until boiling, treat to have in the spherical condensation tube to reflux and produce, insulation reaction got Hyperbranched Polymer with Terminal Hydroxyl in 7 hours, slowly drip the MPEG-succinate monoester that make (1) in this system, approximately drip 2 hours, the control temperature of reaction is at 90～120 ℃, reflux water-dividing, reacted 4～6 hours, then underpressure distillation desolventizing and excessive (1) product obtain the modified ultra-branching polymkeric substance that end contains a small amount of hydroxyl and a large amount of R bases;
(3) 0.02mol polyethers 2000 is added in the reaction vessel of dry cleansings, under the vacuum tightness about-0.092MP, open circulating condensing water, open stirring.The control temperature is about 90 ℃, and dehydration is cooled to 50 ℃ until substantially anhydrous out the time on the condenser.At N
2Protection is lower, opens stirring, slowly drips 0.045molIPDI in the complete material of above-mentioned dehydration; strict control temperature of reaction in case the generation of implode reaction dropwises, then slowly is warming up to 80～82 ℃ in 30min about 50 ℃; keep this temperature range, polymerization under atmospheric pressure reaction 2 hours.Then be cooled to 50 ℃, in system, drip 0.045molKH550, be warmed up to 80 ℃ after dropwising and react half an hour, add proper amount of acetone and regulate viscosity, stop to add, after system is down to room temperature, add the hyperbranched polymer 0.006mol that (2) make, add 0.5% catalyzer dibutyl tin dilaurate of reaction monomers total mass, be warmed up to 80 ℃, rotating speed is brought up to 3000r/min, reacts 1 hour.Reaction is cooled to room temperature after finishing, the mixing solutions emulsification of adding 0.02mol hydrazine hydrate and 5.56mol water 1 hour.Close N
2Intake valve is opened vacuum system, under the condition about vacuum tightness-0.092MP, and 50 ℃ of lower underpressure distillation desolventizing in 2～3 hours and unreacted monomer.Then close vacuum system, open N
2Intake valve is at N
2Protection is lower, makes system recover normal pressure, is discharged in the plastic containers, obtains hyperbranched non-ionic water polyurethane emulsion.
Soaking the water of joining adding 50wt% in the tank, open stirring, slowly add the hyperbranched non-ionic water polyurethane of the above-mentioned preparation of 10wt% as membrane-forming agent, stir and slowly add successively the 0.4wt% lubricant after 30 minutes, the 0.2wt% static inhibitor, add at last remaining water and with the PH conditioning agent PH is regulated 4～7, obtain treating compound.
The glass fibre reinforced plastic PA66 of processing with this treating compound, wherein the massfraction of glass fibre is 30%, the experiment test interface binding intensity is extracted in utilization, according to standard GB/T1447-2005, measures its tensile strength, elongation at break, according to standard GB/T1449-2005, measure its flexural strength, according to standard GB/T1451-2005, measure its shock strength, the results are shown in Table 1.
Example 4
(1) takes by weighing the 0.20mol Succinic anhydried, 0.20mol poly glycol monomethyl ether (350) is dissolved in respectively among an amount of DMAc, then adds there-necked flask, adds 0.5% catalyzer DMAP of reaction monomers total mass in the flask, be warmed up to 70 ℃ of reactions 4 hours, make MPEG-succinate monoester solution.
(2) take by weighing 0.15mol Succinic anhydried, 0.15mol diisopropanolamine (DIPA), at first diisopropanolamine (DIPA) is dissolved among an amount of DMAc, pour into after the dissolving in the there-necked flask with magnetic stirring apparatus, again Succinic anhydried is dissolved with an amount of DMAc, then it slowly is added drop-wise in the there-necked flask, stirs while dripping, approximately drip 0.5 hour, normal-temperature reaction 3 hours obtains AB
2The type monomer.In above-mentioned system, add first 60 mL toluene (toluene is the band aqua), add 0.05mol core molecule TriMethylolPropane(TMP), add reaction monomers 0.5% catalyzer tosic acid, then begin heating, until boiling, treat to have in the spherical condensation tube to reflux and produce, insulation reaction got Hyperbranched Polymer with Terminal Hydroxyl in 7 hours, slowly drip the MPEG-succinate monoester that make (1) in this system, approximately drip 2 hours, the control temperature of reaction is at 90～120 ℃, reflux water-dividing, reacted 4～6 hours, then underpressure distillation desolventizing and excessive (1) product obtain the modified ultra-branching polymkeric substance that end contains a small amount of hydroxyl and a large amount of R bases.
(3) 0.01mol polyethers 2000 and 0.01mol polyethers 210 added in the reaction vessel of dry cleansings, under the vacuum tightness about-0.092MP, open circulating condensing water, open stirring.The control temperature is about 90 ℃, and dehydration is cooled to 50 ℃ until substantially anhydrous out the time on the condenser.At N
2Protection is lower, opens stirring, slowly drips 0.045molIPDI in the complete material of above-mentioned dehydration; strict control temperature of reaction in case the generation of implode reaction dropwises, then slowly is warming up to 80～82 ℃ in 30min about 50 ℃; keep this temperature range, polymerization under atmospheric pressure reaction 2 hours.Then be cooled to 50 ℃, in system, drip 0.045molKH550, be warmed up to 80 ℃ after dropwising and react half an hour, add proper amount of acetone and regulate viscosity, stop to add, after system is down to room temperature, add the hyperbranched polymer 0.015mol that (2) make, add 0.5% catalyzer dibutyl tin dilaurate of reaction monomers total mass, be warmed up to 80 ℃, rotating speed is brought up to 3000r/min, reacts 1 hour.Reaction is cooled to room temperature after finishing, the mixing solutions emulsification of adding 0.02mol hydrazine hydrate and 5.56mol water 1 hour.Close N
2Intake valve is opened vacuum system, under the condition about vacuum tightness-0.092MP, and 50 ℃ of lower underpressure distillation desolventizing in 2～3 hours and unreacted monomer.Then close vacuum system, open N
2Intake valve is at N
2Protection is lower, makes system recover normal pressure, is discharged in the plastic containers, obtains hyperbranched non-ionic water polyurethane emulsion.
Soaking the water of joining adding 50wt% in the tank, open stirring, slowly add the hyperbranched non-ionic water polyurethane of the above-mentioned preparation of 10wt% as membrane-forming agent, stir and slowly add successively the 0.4wt% lubricant after 30 minutes, the 0.2wt% static inhibitor, add at last remaining water and with the PH conditioning agent PH is regulated 4～7, obtain treating compound.
The glass fibre reinforced plastic PA66 of processing with this treating compound, wherein the massfraction of glass fibre is 30%, the experiment test interface binding intensity is extracted in utilization, according to standard GB/T1447-2005, measures its tensile strength, elongation at break, according to standard GB/T1449-2005, measure its flexural strength, according to standard GB/T1451-2005, measure its shock strength, the results are shown in Table 1.
Example 5
(1) takes by weighing the 0.22mol Succinic anhydried, 0.22mol poly glycol monomethyl ether (350) is dissolved in respectively among an amount of DMAc, then adds there-necked flask, adds 0.5% catalyzer DMAP of reaction monomers total mass in the flask, be warmed up to 70 ℃ of reactions 4 hours, make MPEG-succinate monoester solution;
(2) take by weighing 0.21mol Succinic anhydried, 0.21mol diisopropanolamine (DIPA), at first diisopropanolamine (DIPA) is dissolved among an amount of DMAc, pour into after the dissolving in the there-necked flask with magnetic stirring apparatus, again Succinic anhydried is dissolved with an amount of DMAc, then it slowly is added drop-wise in the there-necked flask, stirs while dripping, approximately drip 0.5 hour, normal-temperature reaction 3 hours obtains AB
2The type monomer.In above-mentioned system, add first 60 mL toluene (toluene is the band aqua), add 0.01mol core molecule TriMethylolPropane(TMP), the 0.5% catalyzer tosic acid that adds the reaction monomers total mass, then begin heating, until boiling, treat to have in the spherical condensation tube to reflux and produce, insulation reaction got Hyperbranched Polymer with Terminal Hydroxyl in 7 hours, slowly drip the MPEG-succinate monoester that make (1) in this system, approximately drip 2 hours, the control temperature of reaction is at 90～120 ℃, reflux water-dividing, reacted 4～6 hours, then underpressure distillation desolventizing and excessive (1) product obtain the modified ultra-branching polymkeric substance that end contains a small amount of hydroxyl and a large amount of R bases;
(3) 0.02mol polyethers 2000 is added in the reaction vessel of dry cleansings, under the vacuum tightness about-0.092MP, open circulating condensing water, open stirring.The control temperature is about 90 ℃, and dehydration is cooled to 50 ℃ until substantially anhydrous out the time on the condenser.At N
2Protection is lower, opens stirring, slowly drips 0.045molIPDI in the complete material of above-mentioned dehydration; strict control temperature of reaction in case the generation of implode reaction dropwises, then slowly is warming up to 80～82 ℃ in 30min about 50 ℃; keep this temperature range, polymerization under atmospheric pressure reaction 2 hours.Then be cooled to 50 ℃, in system, drip 0.045molKH550, be warmed up to 80 ℃ after dropwising and react half an hour, add proper amount of acetone and regulate viscosity, stop to add, after system is down to room temperature, add the hyperbranched polymer 0.015mol that (2) make, add 0.5% catalyzer dibutyl tin dilaurate of reaction monomers total mass, be warmed up to 80 ℃, rotating speed is brought up to 3000r/min, reacts 1 hour.Reaction is cooled to room temperature after finishing, the mixing solutions emulsification of adding 0.02mol hydrazine hydrate and 5.56mol water 1 hour.Close N
2Intake valve is opened vacuum system, under the condition about vacuum tightness-0.092MP, and 50 ℃ of lower underpressure distillation desolventizing in 2～3 hours and unreacted monomer.Then close vacuum system, open N
2Intake valve is at N
2Protection is lower, makes system recover normal pressure, is discharged in the plastic containers, obtains hyperbranched non-ionic water polyurethane emulsion.
Soaking the water of joining adding 50wt% in the tank, open stirring, slowly add the hyperbranched non-ionic water polyurethane of the above-mentioned preparation of 10wt% as membrane-forming agent, stir and slowly add successively the 0.4wt% lubricant after 30 minutes, the 0.2wt% static inhibitor, add at last remaining water and with the PH conditioning agent PH is regulated 4～7, obtain treating compound.
The glass fibre reinforced plastic PA66 of processing with this treating compound, wherein the massfraction of glass fibre is 30%, the experiment test interface binding intensity is extracted in utilization, according to standard GB/T1447-2005, measures its tensile strength, elongation at break, according to standard GB/T1449-2005, measure its flexural strength, according to standard GB/T1451-2005, measure its shock strength, the results are shown in Table 1.
Adopt commercially available anion-type water-thinned polyurethane membrane-forming agent in contrast, the glass fibre performance that obtains sees Table 1
The above-mentioned example the performance test results of table 1
Claims (10)
1. hyperbranched non-ionic water polyurethane is characterized in that obtaining by following steps:
1. Succinic anhydried and poly glycol monomethyl ether reaction are generated the hydrophilic polymer of holding carboxyl,
2. add the hydrophilic polymer of the end carboxyl of step in 1. in the Hyperbranched Polymer with Terminal Hydroxyl, reaction gets the modified ultra-branching polymkeric substance;
3. the modified ultra-branching polymer reaction that 2. polyether glycol, isocyanic ester, silane coupling agent, step is obtained to isocyanate group content is 0%, and aftertreatment gets hyperbranched non-ionic water polyurethane.
2. hyperbranched non-ionic water polyurethane according to claim 1, it is characterized in that modified ultra-branching Polymer-supported chain end contain hydroxyl and
, its mol ratio is 1:2～11.
3. hyperbranched non-ionic water polyurethane according to claim 1 is characterized in that the hydroxyl in the modified ultra-branching polymkeric substance and the mol ratio of isocyanate group are 1:1 ~ 1.5 in the step (3), and the mol ratio of silane coupling agent and isocyanic ester is 1:1.
4. hyperbranched non-ionic water polyurethane according to claim 1 is characterized in that core molecule and the AB of described Hyperbranched Polymer with Terminal Hydroxyl
2The first-generation terminal hydroxy group polyesteramide that monomer obtains respectively according to 1:3,1:9 or 1:21 molar ratio reaction, s-generation terminal hydroxy group polyesteramide or third generation terminal hydroxy group polyesteramide.
5. hyperbranched non-ionic water polyurethane according to claim 5 is characterized in that the mol ratio of the hydrophilic polymer of the end carboxyl during the core molecule of synthetic Hyperbranched Polymer with Terminal Hydroxyl during step 2. and step are 1. is 1:1 ~ 22.
6. hyperbranched non-ionic water polyurethane according to claim 5 is characterized in that AB
2Monomer is synthetic according to mol ratio 1:1 by Succinic anhydried and diisopropanolamine (DIPA).
7. hyperbranched non-ionic water polyurethane according to claim 5 is characterized in that used poly glycol monomethyl ether model is mpeg 3 50 ~ 700, and isocyanic ester is aliphatic isocyanates IPDI.
8. the application of the described hyperbranched non-ionic water polyurethane of claim 1-7 in glass fiber infiltration agent.
9. application according to claim 8 is characterized in that containing in the glass fiber infiltration agent the hyperbranched non-ionic water polyurethane of 8 ~ 12% membrane-forming agent emulsion weight percents.
10. application according to claim 9 is characterized in that also containing in the glass fiber infiltration agent 0.2 ~ 0.5wt% lubricant, 0.1 ~ 0.3wt% static inhibitor, and the PH conditioning agent of 0.1 ~ 0.2wt%, surplus is water.
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