CN105294986A - Solid-state hypocrystalline unsaturated polyurethane prepolymer and preparation method thereof - Google Patents
Solid-state hypocrystalline unsaturated polyurethane prepolymer and preparation method thereof Download PDFInfo
- Publication number
- CN105294986A CN105294986A CN201510715519.2A CN201510715519A CN105294986A CN 105294986 A CN105294986 A CN 105294986A CN 201510715519 A CN201510715519 A CN 201510715519A CN 105294986 A CN105294986 A CN 105294986A
- Authority
- CN
- China
- Prior art keywords
- unsaturated
- solid
- state
- alcohol
- prepolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/6715—Unsaturated monofunctional alcohols or amines
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2150/00—Compositions for coatings
- C08G2150/20—Compositions for powder coatings
Abstract
The invention discloses a solid-state hypocrystalline unsaturated polyurethane prepolymer and a preparation method thereof. The melting range of the polyurethane prepolymer ranges from 50 DEG C to 145 DEG C, the melt viscosity is smaller than or equal to 100 mpa*s, the number-average molecular weight ranges from 250 to 5000, the unsaturation degree is 0.3-6 mmol/g, and the solid-state hypocrystalline unsaturated polyurethane prepolymer is prepared through reaction with alkyl-chain-base dihydric alcohol, polyisocyanate and unsaturated alcohol and ether stop ends being reaction substances and NCO/OH equivalence ratio being 0.8-1.2. The prepolymer is a solid-state polyurethane prepolymer meeting the construction characteristic requirement, the melting range of the solid-state polyurethane prepolymer is 50-145 DEG C, the prepolymer has good stability in the storage process and has low enough melt viscosity, and therefore when the prepolymer and resin components containing the prepolymer are applied to the surface of a base material, excellent levelling property is achieved, and the unsaturation degree of a resin system is effectively compensated for in the light/heat curing process.
Description
Technical field
The present invention relates to blocked polyurethane prepolymers field and polyurethane prepolymer hypocrystalline immobilization field, be specifically related to solid-state semicrystalline unsaturated polyurethanes prepolymer, relate to the preparation method of this prepolymer simultaneously.
Background technology
End-sealed type polyurethane prepolymer is seen in coating ingredients at present and is reported as master, as US5, and 155,154, US4,977,201, US5,087,664, EP884341, EP583377, US5,741,824, JP2003-268302, WO2008/049857, WO2006/007273 and WO2011/069969 etc., but these polyurethane prepolymers exist with liquid or highly viscous state, the fields such as the scope of application is limited to sizing agent, liquid coating, the unsaturated light/thermofixation Application Areas of the low sticky state of processing under not being suitable for Low Temperature Thermal state or solid-state system.
Light/heat curable powder coating is the environmental protection coating material with broad mass market prospect, and light/heat curable powder coating is coated to substrate surface with pulverulence, through heated baking melt-flow Heisei film, finally crosslinking curing film forming under UV-irradiation.Should use up/base material of heat curable powder coating is generally temperature-sensitive material as MDF sheet material and plastic rubber substrate, and the temperature for heating and melting levelling has strict restriction, general thermal treatment temp≤150 DEG C.
3D printed material such as commercial thermoplastic polyurethane elastomer (TPU) adopts Fused Deposition Modeling technique (FDM) unsaturated polyurethanes prepolymer material, and the bond properties of formed material and ropiness determine the workability of work material and the performance of FDM handicraft product.CN201410005541.3 adopts polyolefine, tenderizer etc. to obtain thermoplastic elastic in Polyurethane Thermoplastic Elastomer, polyolefins comprises maleic anhydride graft styrene-ethylene-butylene-styrene multipolymer (MA-g-SEBS) etc. as main elastomeric component, but widely apply polyolefine as formed material component, when can cause melt extruding, the ropiness of material, thread apparent property and adhesion etc. are unsatisfactory.
Summary of the invention
An object of the present invention is to provide a kind of solid-state semicrystalline unsaturated polyurethanes prepolymer.This prepolymer is based on developing the adaptive perfect of polyurethane prepolymer range of application, further improvement is made to the viscosity of polyurethane composition system and stability in storage, that develops meets the solid polyurethane prepolymer with 50 DEG C of-145 DEG C of melting ranges that construction property requires, it not only shows satisfactory stability in storage process, also have when enough low melt viscosity makes prepolymer and the resin Composition containing this prepolymer be applied in substrate surface and obtain excellent levelling property, the degree of unsaturation of effective compensation resin system in light/curing process.
Two of object of the present invention is the preparation method providing above-mentioned solid-state semicrystalline unsaturated polyurethanes prepolymer.
One of the object of the invention is achieved through the following technical solutions: a kind of solid-state semicrystalline unsaturated polyurethanes prepolymer, the melting range of polyurethane prepolymer 50 DEG C-145 DEG C, melt viscosity≤100mpa.s, number-average molecular weight scope is between 250 to 5000, degree of unsaturation is 0.3-6mmol/g, makes for reactive material carries out reaction by NCO/OH equivalence ratio 0.8 to 1.2 with alkane chain base dibasic alcohol, polyisocyanates and ether capped dose of unsaturated alcohol.
Polyurethane prepolymer provided by the invention has 50 DEG C of-140 DEG C of melting ranges, is hypocrystalline water white transparency or the oyster white solid matter of stable existence below melting range.The number-average molecular weight scope of this prepolymer preferably >=300 and≤4000, melt viscosity preferably≤50mpa.s.This polyurethane prepolymer can be used for preparation and comprises at least one acrylic resin as unsaturated polyester acrylic resin and/or epoxy acrylic resin, with the powder paint compositions of other compositions optional and additive, realize fused coating levelling by applying this coating composition thermal treatment of one deck at substrate surface, this coating composition layer of light/thermofixation obtains a solidified coating.This prepolymer also can be applicable to increase material manufacturing processed simultaneously, effectively can improve polyurethane elastomer in workabilities such as the bond properties of construction process and ropinesses after melt extruding.
In reactive material of the present invention, described alkane chain base dibasic alcohol is at least the C with symmetrical structure
2to C
12alkane chain base dibasic alcohol in one, described polyisocyanates at least comprises hexamethylene diisocyanate, and ether capped dose of described unsaturated alcohol is the monohydroxy end-capping reagent containing unsaturated double-bond.Above-mentioned reactive material is preferably reacted with NCO/OH equivalence ratio 0.9-1.1, and preferred NCO/OH equivalence ratio is 0.95-1.05.
The C with symmetrical structure of the present invention
2to C
12alkane chain base dibasic alcohol there is C
2to C
12symmetry carbochain, applicable alkane chain base dibasic alcohol includes but not limited to following compound: ethylene glycol, Diethylene Glycol, 1,3 propylene glycol, 2-methyl isophthalic acid, ammediol, 2，2-dimethyl-1，3-propanediol, BDO, 1,5-PD, 1,6-hexylene glycol, 1,4 cyclohexane dimethanol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecane, 1,12-dodecanediol etc.The alkane chain base dibasic alcohol of above-mentioned symmetrical structure, except participating in reaction with the pure form of monomer, also can meet the needs of reaction with two kinds and above monomer mixture form.When two kinds of alkane chain base glycol monomer participate in reaction, monomer equivalent proportional range is preferably 0.5:1-3:1, and more preferably scope is 1:1-2:1.When three kinds and above alkane chain base glycol monomer participate in above-mentioned reaction, preferred equivalents ratio is equivalent ratio consumption.
The form of mixtures of the pure form of monomer or more different monomers combination is adopted to participate in reaction, and the hydroxyl total amount that provides of alkane chain base dibasic alcohol accounts for the equivalents ratio of all hydroxyls participating in reaction system, to the melting range adjustment of polyurethane prepolymer of the present invention, there is key effect.C in reaction system
2-C
12alkane chain base dibasic alcohol consumption, its equivalents ratio accounts for OH population proportion scope and is no more than 60%, preferably more than 50%, more preferably no more than 30%.
Polyisocyanates of the present invention at least comprises a kind of hexamethylene diisocyanate.Hexamethylene diisocyanate or its isomer of known or available any one form all can adopt, and comprise monomeric hexamethylene vulcabond (monomer HDI) and polymeric hexamethylene diisocyanate.Polymeric hexamethylene diisocyanate is as hexamethylene diisocyanate trimer (PHDI).The NCO equivalents ratio of haplotype and/or polymeric hexamethylene diisocyanate accounts for the NCO population proportion of reaction system for being not less than 40%, is preferably not less than 50%, is more preferably and is not less than 70%, be particularly preferably not less than 80%.
Described polyisocyanates also can comprise diphenylmethanediisocyanate (MDI) and/or Toluene-2,4-diisocyanate, 4-vulcabond (TDI), the diphenylmethanediisocyanate (MDI) of known or available any one form, Toluene-2,4-diisocyanate, 4-vulcabond (TDI) or its isomer all can adopt, comprise monomeric diphenylmethane vulcabond (MDI), haplotype Toluene-2,4-diisocyanate, 4-vulcabond (TDI), polymeric diphenylmethane vulcabond (PMDI) and polymer-type Toluene-2,4-diisocyanate, 4-vulcabond (PTDI) etc.Available diphenylmethanediisocyanate isomer comprises 2,4-diphenylmethanediisocyanate, 4,4-diphenylmethanediisocyanates, Toluene-2,4-diisocyanate, the oligopolymer of 6-vulcabond and their correspondences and mixture.As diphenylmethanediisocyanate (MDI) and Toluene-2,4-diisocyanate in reaction, when 4-vulcabond (TDI) is used in combination, both NCO equivalents ratio are 95/5-65/35, are preferably 90/10-70/30, are more preferably 85/15-75/25.
Described diphenylmethanediisocyanate (MDI) and/or Toluene-2,4-diisocyanate, the NCO overall equivalent ratio that the total yield ratio of 4-vulcabond (TDI) accounts for reaction system is no more than 60%, preferably be no more than 40%, more preferably less than 30%, be particularly preferably no more than 20%.
Prepare unsaturated polyurethanes prepolymer, at least should use ether capped dose of a kind of unsaturated alcohol, comprise vinyl alcohol ethers end-capping reagent, allyl alcohol ethers end-capping reagent and propenyl alcohol ethers end-capping reagent etc., what meet end-blocking service requirements comprises hydroxy butyl vinyl ether, cyclohexyl-1,4-dimethanol monovinyl ether, glycol divinyl ether, polyoxyethylene glycol mono vinyl ether, allyl polyglycol, ethylene glycol monoallyl ether etc., they can be used alone and also can be used in combination.When using above-mentioned two class end-capping reagent, both equivalents ratio are 0.5:1-1.5:1, and preferred scope is 0.8:1-1.2:1 simultaneously.
The present invention regulates the degree of unsaturation of product polyurethane prepolymer to meet various activity of curing reaction and to realize all kinds of curing performance by the usage ratio changing unsaturated alcohol ethers end-capping reagent, but too high degree of unsaturation easily induces the double bond of the reaction process of this prepolymer of preparation or the product course of processing unstable, and suitable polyurethane prepolymer degree of unsaturation is the degree of unsaturation of prepolymer is 0.3-6mmol/g.The OH total yield proportional range that the total yield ratio of end-capping reagent accounts for reaction system is 5%-95%, and preferred scope is 30-85%, and more preferably scope is 50%-85%.
The preparation method of solid-state semicrystalline unsaturated polyurethanes prepolymer of the present invention, under catalyzer and stopper exist, polyisocyanates and alkane chain base dibasic alcohol carry out first stage reaction, and range of reaction temperature is 30 DEG C-160 DEG C; Described polyisocyanates and alkane chain base diol reaction completely after, keep the terminal temperature of first stage reaction, add ether capped dose of unsaturated alcohol and carry out subordinate phase reaction, the OH functional group of ether capped dose of unsaturated alcohol and the NCO functional group of reaction system remnants react, and obtain solid-state semicrystalline unsaturated polyurethanes prepolymer.
Three kinds of reactive modes that feed intake that in first stage reaction, described polyisocyanates enters symmetrical alkane chain base dibasic alcohol system in the mode dripped, symmetrical alkane chain base dibasic alcohol enters polyisocyanates system and symmetrical alkane chain base dibasic alcohol and the blended intensification of polyisocyanates room temperature in the mode dripped are all can be used as alternative technique.Ether capped dose of described unsaturated alcohol feeds intake in the mode dripped.
The alternative synthetic catalyst of polyurethane preformed polymer comprises Titanium series catalyst and organic tin catalyzer etc., and preferred catalyzer is organic tin catalyzer.Described stopper is hydroquinone monomethyl ether.
Semicrystalline polyurethane prepolymer provided by the invention has 50 DEG C of-140 DEG C of melting ranges, be hypocrystalline water white transparency or the oyster white solid matter of stable existence below melting range, viscosity≤100mpa.s after melting, have and be applied to FDM and increase the potentiality that material manufactures, it effectively can improve polyurethane elastomer in workabilities such as the bond properties of construction process and ropinesses after melt extruding.It is as coating and adhesive composition component, under heating or UV Light condition melting by and the composition such as coating/binding agent in other component reaction and a solidified coating is provided, be especially used in light/heat curable powder coating composition and 3D prints the fields such as the component in light/thermally curable resin composition.And due to the watery fusion of this prepolymer and low melting viscosity characteristic, be conducive to a difficult problem for the watery fusion levelling property solving light/heat curable powder paint coatings, ensure solidification effect as effective compensation component during film UV-light/thermofixation simultaneously.
Embodiment
The raw material that embodiment uses is as follows:
Hexamethylene diisocyanate trimer (PHDI), Japanese Asahi Chemical Industry, NCO content >=20%;
Hexamethylene diisocyanate (HDI), German BASF, NCO content >=49.7%;
2,4-diphenylmethanediisocyanate monomer (MDI), Bayer Bitterfeld GmbH, NCO content >=33.6%;
Toluene-2,4-diisocyanate, 4-vulcabond (TDI), Bayer Bitterfeld GmbH, NCO content >=47%;
Alkane chain base dibasic alcohol, catalyzer, stopper, commercially available.
comparative example 1
The hexamethylene diisocyanate trimer (PHDI) of 75.1g and dibutyltin dilaurate catalyst 0.03g are added the reactor of the led to nitrogen being with stirring rake simultaneously, be slowly warming up to 60 DEG C, temperature-rise period keeps logical nitrogen and whipped state.The hydroxy butyl vinyl ether (HBVE) of slow dropping 48.9g enters hexamethylene diisocyanate trimer, drips process control rate of addition and avoids temperature of reaction system more than 80 DEG C, and the process that drips keeps logical nitrogen and whipped state; 100 DEG C-120 DEG C are slowly warming up to after dripping hydroxy butyl vinyl ether (HBVE), insulating process keeps logical nitrogen and whipped state, be incubated discharging after 1 ~ 2 hour, the crisp hard object matter of water white transparency after room temperature cooling, melting range is 51-53 DEG C, melt viscosity≤10mpa.s, prepolymer degree of unsaturation 3.32mmol/g, number-average molecular weight 853.
embodiment 1
Keep logical nitrogen and whipped state, 84.1g hexamethylene diisocyanate monomer (HDI), dibutyltin dilaurate catalyst 0.05g and 0.01g hydroquinone monomethyl ether stopper are added simultaneously the reactor of the led to nitrogen being with stirring rake, slowly be warming up to 60 DEG C, 1 of slow dropping 29.5g, 6-hexylene glycol (1,6-HDO), drips process control rate of addition and avoids temperature of reaction system more than 80 DEG C, slowly be warming up to 120 DEG C, be incubated and within 1-2 hour, complete first stage reaction; The glycol divinyl ether (EGVE) of slow dropping 44.1g enters first stage reaction system, drips process control rate of addition and avoids temperature of reaction system to be no more than 130 DEG C; Slowly heat up and keep temperature 150 DEG C ~ 160 DEG C after dripping glycol divinyl ether, discharging after insulation 1h, the crisp hard object matter of oyster white after room temperature cooling, melting range is 135-143 DEG C, melt viscosity≤50mpa.s, prepolymer degree of unsaturation 3.17mmol/g, number-average molecular weight 316.
embodiment 2
Keep logical nitrogen and whipped state, 67.3g hexamethylene diisocyanate monomer (HDI), dibutyltin dilaurate catalyst 0.04g and 0.01g hydroquinone monomethyl ether stopper are added simultaneously the reactor of the led to nitrogen being with stirring rake, slowly be warming up to 60 DEG C, the ethylene glycol of slow dropping 6.2g, dripping process control rate of addition avoids temperature of reaction system more than 80 DEG C, slowly be warming up to 120 DEG C, be incubated and within 1-2 hour, complete first stage reaction; The glycol divinyl ether (EGVE) of slow dropping 52.9g enters first stage reaction system, drips process control rate of addition and avoids temperature of reaction system more than 125 DEG C; Slowly heat up and keep temperature 125 DEG C ~ 130 DEG C after dripping glycol divinyl ether, discharging after insulation 1h, white crisp hard object matter after room temperature cooling, melting range is 115-118 DEG C, melt viscosity≤50mpa.s, prepolymer degree of unsaturation 4.74mmol/g, number-average molecular weight 315.
embodiment 3
Keep logical nitrogen and whipped state, by 108.1g hexamethylene diisocyanate monomer (HDI), 40.3g2,4-diphenylmethanediisocyanate monomer (2,4-MDI), dibutyltin dilaurate catalyst 0.07g and 0.01g hydroquinone monomethyl ether stopper add the reactor of the led to nitrogen being with stirring rake simultaneously, slowly be warming up to 60 DEG C, 1 of slow dropping 12.2g, 6-hexylene glycol (1.6-HDO), dripping process control rate of addition avoids temperature of reaction system more than 80 DEG C, slowly be warming up to 120 DEG C, be incubated and within 1-2 hour, complete first stage reaction; The glycol divinyl ether (EGVE) of slow dropping 123.8g enters first stage reaction system, drips process control rate of addition and avoids temperature of reaction system more than 125 DEG C; Slowly heat up and keep temperature 120 DEG C-125 DEG C after dripping glycol divinyl ether, discharging after insulation 1h, white crisp hard object matter after room temperature cooling, melting range is 104 ~ 106 DEG C, melt viscosity≤40mpa.s, prepolymer degree of unsaturation 5.12mmol/g, number-average molecular weight 387.
embodiment 4
Keep logical nitrogen and whipped state, 135.2g hexamethylene diisocyanate monomer (HDI), dibutyltin dilaurate catalyst 0.07g and 0.01g hydroquinone monomethyl ether stopper are added simultaneously the reactor of the led to nitrogen being with stirring rake, be warming up to 60 DEG C, 1 of rear slowly dropping 5.9g, the blend of the neopentyl glycol of 6-hexylene glycol and 5.2g, dripping process control rate of addition avoids temperature of reaction system more than 80 DEG C, slowly be warming up to 120 DEG C, be incubated and within 1-2 hour, complete first stage reaction; The glycol divinyl ether (EGVE) of slow dropping 124.1g enters first stage reaction system, drips process control rate of addition and avoids temperature of reaction system more than 125 DEG C; Slowly heat up and keep temperature 120 DEG C-125 DEG C after dripping glycol divinyl ether, discharging after insulation 1h, white crisp hard object matter after room temperature cooling, melting range 83 ~ 86 DEG C, melt viscosity≤50mpa.s, prepolymer degree of unsaturation 5.21mmol/g, number-average molecular weight 336.
embodiment 5
Keep logical nitrogen and whipped state, by 100.9g hexamethylene diisocyanate monomer (HDI), the diphenylmethanediisocyanate (MDI) of 37.5g, the Toluene-2,4-diisocyanate of 8.7g, 4-vulcabond (TDI), dibutyltin dilaurate catalyst 0.07g and 0.01g hydroquinone monomethyl ether stopper add the reactor of the led to nitrogen being with stirring rake simultaneously, slowly be warming up to 60 DEG C, 1 of slow dropping 11.9g, 6-hexylene glycol, dripping process control rate of addition avoids temperature of reaction system more than 80 DEG C, slowly be warming up to 120 DEG C, be incubated and within 1-2 hour, complete first stage reaction, the glycol divinyl ether (EGVE) of slow dropping 123.3g enters first stage reaction system, drips process control rate of addition and avoids temperature of reaction system more than 125 DEG C, slowly heat up and keep temperature 120 DEG C-125 DEG C after dripping glycol divinyl ether, discharging after insulation 1h, white crisp hard object matter after room temperature cooling, melting range is 75 ~ 78 DEG C, melt viscosity≤40mpa.s, prepolymer degree of unsaturation 4.95mmol/g, molecular weight 403.
embodiment 6
Keep logical nitrogen and whipped state, 67.3g hexamethylene diisocyanate monomer (HDI), dibutyltin dilaurate catalyst 0.04g and 0.01g hydroquinone monomethyl ether stopper are added simultaneously the reactor of the led to nitrogen being with stirring rake, slowly be warming up to 60 DEG C, the ethylene glycol (EG) of slow dropping 6.2g, dripping process control rate of addition avoids temperature of reaction system more than 80 DEG C, slowly be warming up to 120 DEG C, be incubated and within 1-2 hour, complete first stage reaction; The slow glycol divinyl ether (EGVE) dripping 31.8g enters first stage reaction system with 24.6g ethylene glycol monoallyl ether (EGAE), drips process control rate of addition and avoids temperature of reaction system more than 120 DEG C; Slowly heat up and keep temperature 120 DEG C ~ 125 DEG C after dripping glycol divinyl ether, discharging after insulation 1h, white crisp hard object matter after room temperature cooling, melting range is 96 ~ 98 DEG C, melt viscosity≤50mpa.s, prepolymer degree of unsaturation 4.62mmol/g, relative molecular weight 324.
comparative example 2
There is agitator, thermometer and be connected with in the four-hole bottle of nitrogen, the terminal carboxyl polyester resin (Guangzhou Kinte Material Technology Co., Ltd.) 1000g with 30-35mgKOH/g acid number is heated to 230 DEG C of insulations, 3g amines catalyst is added when being cooled to 190 DEG C after the complete melting of resin, after continuing to be cooled to 170 DEG C ~ 180 DEG C, slow dropping 90.6g glycidyl methacrylate (GMA, chemical pure, commercially available, add 0.03% stopper).Discharging after 180-185 DEG C of insulation 30min after GMA dropwises, the viscosity obtaining the polyester acrylate with double bond is 22000mpa s(140 DEG C), 1200mpa s(200 DEG C).The degree of unsaturation that iodimetry,iodometry measures product is 0.52mmol/g.
comparative example 3
There is agitator, thermometer and be connected with in the four-hole bottle of nitrogen, the epoxy resin (Guangzhou Hong Chang Electron Material Co., Ltd) 600g with 450-500g/eq epoxy equivalent (weight) is jointly heated to 150 DEG C with 1.2g amines catalyst and is incubated, after being cooled to 110-115 DEG C after the complete melting of resin, slow dropping 89.5g(methyl) vinylformic acid (chemical pure, commercially available, add 0.02% stopper).Controlling rate of addition avoids temperature more than 130 DEG C, discharging after 120-125 DEG C of insulation 30min after (methyl) vinylformic acid dropwises, and the viscosity obtaining undersaturated epoxy acrylate is 650mpa s(140 DEG C), 430mpa s(200 DEG C).The degree of unsaturation that iodimetry,iodometry measures product is 1.37mmol/g.
experimental example
Evaluate the effect of solid-state semicrystalline unsaturated polyurethanes prepolymer in light/heat curable powder coating, according to the form below takes component, and extrude through forcing machine mixing after mixing precomminution, extrudate obtains photocuring powder coating through pulverizer grinding and sieving again.Use tribo-gun by paint spay-coating in through eliminate rust oil removing aluminium sheet on.
Using comparative example 2 resin and comparative example 3 resin as the matrix resin part of light/heat curable powder coating, add the solid-state unsaturated polyurethanes prepolymer of semicrystalline, in conjunction with comprising initiator, flow agent, pigment, condiment, st-yrax composition light/heat curable powder coating.
Powder coating component comprises: light trigger, Irgacure184D, BASF; Thermal initiator, TrigonoxBPIC-C75, AKZONOBEL; Flow agent, RheoflowPLP-100, KSCNT; Titanium dioxide, barium sulfate, st-yrax, commercially available.
The solidification of photocuring powder coating, coating is carried out photocuring (UV energy 1500mJ/cm after being placed in the Electric heat oven interior baking 10min being set as 140 DEG C by coated aluminium sheet
2), under the coating room temperature after photocuring, cooling can obtain film sample, for carrying out film performance test.
The solidification of heat curable powder coating, coated aluminium sheet be placed in be set as 140 DEG C Electric heat oven in after baking-curing 10min, under room temperature, cooling can obtain film sample, for carrying out film performance test.
the measurement of the horizontal flow of light/heat curable powder coating
The melt-flow levelling of the horizontal flow reflection coating of powder coating is the correlation metric of the apparent planeness of film.
Configure light/heat curable powder coating by a certain percentage, get powder coating compressing tablet (diameter the is 15mm) demoulding afterwards of 1g.To obtain thin discs (diameter 15mm) to be placed in and to be set on the hot-plate of temperature, and constantly expand after (melting) 10min until thin discs, measure the disk diameter d expanded with compasses, this diameter d is horizontal flow, unit mm.
Evaluate solid-state semicrystalline unsaturated polyurethanes prepolymer fusion sediment increase improve Polyurethane Thermoplastic Elastomer (TPU) formed material in manufacture process (FDM) technology ropiness can with fusible effect.According to the form below is configured to shaped material composition, uses fusion sediment type 3D printing device printed material after melt extruding wire drawing, coordinates between UV layer and scans, and obtains finished product, carry out performance test after solidification cooling.
Formed material component comprises: polyurethane elastomer 1, KratonG series, KratonPerformancePolymersInc; Polyurethane elastomer 2, Tafmer series, Mitsui Chemicals; Polyolefine, PPC polypropylene series, TotalS.A; Light trigger, Irgacure184D, BASF; Tenderizer, Hydrobrite, SonnebornInc; Lubricant, Kemamide series, PMC; Oxidation inhibitor, phosphorous acid esters, commercially available.
The ropiness evaluation of Fused Deposition Modeling (FDM) formed material, is extruded after material molten by 3D printer, extrudes 10 hours continuously, and the number of times of statistics blocking printhead or fracture of wire, number of times is as the index passing judgment on formed material ropiness.
From the result of above-mentioned experiment, contrast the light/heat curing coating formula of untapped prepolymer, the horizontal flow employing the light/heat curing coating of prepolymer of the present invention is significantly improved, and corresponding film performance also improves; The watery fusion of visible prepolymer and low melting viscosity characteristic, solve a difficult problem for the watery fusion levelling property of light/heat curable powder paint coatings.And due to prepolymer provided by the invention be solid, in storage process, not easily there is conglomeration in light/heat curable powder coating.In addition, with the addition of the workability such as the bond properties at construction process that effectively can improve polyurethane elastomer and ropiness of prepolymer of the present invention.
Claims (10)
1. a solid-state semicrystalline unsaturated polyurethanes prepolymer, it is characterized in that, the melting range of this polyurethane prepolymer 50 DEG C-145 DEG C, melt viscosity≤100mpa.s, number-average molecular weight scope is between 250 to 5000, degree of unsaturation is 0.3-6mmol/g, makes for reactive material carries out reaction by NCO/OH equivalence ratio 0.8 to 1.2 with alkane chain base dibasic alcohol, polyisocyanates and ether capped dose of unsaturated alcohol.
2. solid-state semicrystalline unsaturated polyurethanes prepolymer according to claim 1, it is characterized in that, the number-average molecular weight scope of described prepolymer is >=300 and≤4000, and melt viscosity is≤50mpa.s, and described reactive material is reacted with NCO/OH equivalence ratio 0.9-1.1.
3. solid-state semicrystalline unsaturated polyurethanes prepolymer according to claim 1, is characterized in that, described alkane chain base dibasic alcohol is at least the C with symmetrical structure
2to C
12alkane chain base dibasic alcohol in one, described polyisocyanates at least comprises hexamethylene diisocyanate, and ether capped dose of described unsaturated alcohol is the monohydroxy end-capping reagent containing unsaturated double-bond.
4. solid-state semicrystalline unsaturated polyurethanes prepolymer according to claim 1, is characterized in that, the described C with symmetrical structure
2to C
12alkane chain base dibasic alcohol there is C
2to C
12symmetry carbochain; Described hexamethylene diisocyanate comprises monomeric hexamethylene vulcabond and/or polymeric hexamethylene diisocyanate; Ether capped dose of described unsaturated alcohol is vinyl alcohol ethers end-capping reagent, one or more the combination in allyl alcohol ethers end-capping reagent and propenyl alcohol ethers end-capping reagent.
5. solid-state semicrystalline unsaturated polyurethanes prepolymer according to claim 4, it is characterized in that, described alkane chain base dibasic alcohol is ethylene glycol, Diethylene Glycol, 1,3 propylene glycol, 2-methyl isophthalic acid, ammediol, 2,2-dimethyl-1, ammediol, BDO, 1,5-PD, 1,6-hexylene glycol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-ethohexadiol, 1,9-nonanediol, 1, one or more combination in 10-decanediol, 1,11-undecane and 1,12-dodecanediol; Ether capped dose of described unsaturated alcohol is one or more the combination in hydroxy butyl vinyl ether, cyclohexyl-Isosorbide-5-Nitrae-dimethanol monovinyl ether, propenyl ethyl ether, glycol divinyl ether, polyoxyethylene glycol mono vinyl ether, allyl polyglycol and ethylene glycol monoallyl ether.
6. solid-state semicrystalline unsaturated polyurethanes prepolymer according to claim 5, is characterized in that, when two kinds of alkane chain base glycol monomer participate in reaction, monomer equivalent proportional range is 0.5:1-3:1; When the alkane chain base glycol monomer of more than three kinds participate in reaction, each monomer equivalent ratio is equivalent ratio consumption; When ether capped dose of use two class unsaturated alcohol, both equivalents ratio are 0.5:1-1.5:1.
7. the solid-state semicrystalline unsaturated polyurethanes prepolymer according to any one of claim 1-6, is characterized in that, the equivalents ratio of described alkane chain base dibasic alcohol accounts for OH population proportion scope and is no more than 60%; The NCO equivalents ratio of described haplotype and/or polymeric hexamethylene diisocyanate accounts for NCO population proportion scope for being not less than 40%; The OH total yield proportional range that the total yield ratio of ether capped dose of unsaturated alcohol accounts for reaction system is 5%-100%.
8. solid-state semicrystalline unsaturated polyurethanes prepolymer according to claim 7, it is characterized in that, described polyisocyanates also comprises diphenylmethanediisocyanate and/or Toluene-2,4-diisocyanate, 4-vulcabond, described diphenylmethanediisocyanate and/or Toluene-2,4-diisocyanate, the total yield ratio of 4-vulcabond accounts for NCO overall equivalent ratio scope and is no more than 60%; When using diphenylmethanediisocyanate and Toluene-2,4-diisocyanate in reaction, when 4-vulcabond is used in combination, both NCO equivalents ratio are 95/5-65/35.
9. the preparation method of the solid-state semicrystalline unsaturated polyurethanes prepolymer described in any one of claim 1-8, it is characterized in that, under catalyzer and stopper exist, polyisocyanates and alkane chain base dibasic alcohol carry out first stage reaction, and range of reaction temperature is 30 DEG C-160 DEG C; Described polyisocyanates and alkane chain base diol reaction completely after, keep the terminal temperature of first stage reaction, add ether capped dose of unsaturated alcohol and carry out subordinate phase reaction, the OH functional group of ether capped dose of unsaturated alcohol and the NCO functional group of reaction system remnants react, and obtain solid-state semicrystalline unsaturated polyurethanes prepolymer.
10. the preparation method of solid-state semicrystalline unsaturated polyurethanes prepolymer according to claim 9, it is characterized in that, to be described polyisocyanates enter symmetrical alkane chain base dibasic alcohol system in the mode dripped for the reactive mode that feeds intake of described first stage reaction, symmetrical alkane chain base dibasic alcohol enters polyisocyanates system or symmetrical alkane chain base dibasic alcohol and the blended intensification of polyisocyanates room temperature in the mode dripped; Ether capped dose of described unsaturated alcohol feeds intake in the mode dripped.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510715519.2A CN105294986B (en) | 2015-10-29 | 2015-10-29 | A kind of solid-state semicrystalline unsaturated polyurethanes prepolymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510715519.2A CN105294986B (en) | 2015-10-29 | 2015-10-29 | A kind of solid-state semicrystalline unsaturated polyurethanes prepolymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105294986A true CN105294986A (en) | 2016-02-03 |
| CN105294986B CN105294986B (en) | 2018-10-16 |
Family
ID=55192881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510715519.2A Active CN105294986B (en) | 2015-10-29 | 2015-10-29 | A kind of solid-state semicrystalline unsaturated polyurethanes prepolymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105294986B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108893088A (en) * | 2018-06-07 | 2018-11-27 | 太仓萃励新能源科技有限公司 | A kind of PTC function SPUR adhesive |
| CN110300637A (en) * | 2017-02-17 | 2019-10-01 | 巴斯夫欧洲公司 | Reactive thermoplastic polyurethane based on closed isocyanates |
| WO2019199482A1 (en) * | 2018-04-10 | 2019-10-17 | The Procter & Gamble Company | Polymeric materials and articles manufactured there from |
| US10543639B2 (en) | 2016-08-19 | 2020-01-28 | The Procter & Gamble Company | Method for manufacturing a three-dimensional object |
| CN113278125A (en) * | 2021-05-28 | 2021-08-20 | 南京玖泰新材料科技有限公司 | Photo-curing polyurethane and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6028212A (en) * | 1997-12-16 | 2000-02-22 | Morton International, Inc. | Solid vinyl ether terminated urethane curing agent |
| CN102010558A (en) * | 2010-10-11 | 2011-04-13 | 中国海洋石油总公司 | Acrylic acid non-aqueous dispersoid containing amino ester bonds and siloxy groups and preparation method thereof |
| WO2014173861A1 (en) * | 2013-04-26 | 2014-10-30 | Dsm Ip Assets B.V. | Vinyl functionalized urethane resins for powder coating compositions |
-
2015
- 2015-10-29 CN CN201510715519.2A patent/CN105294986B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6028212A (en) * | 1997-12-16 | 2000-02-22 | Morton International, Inc. | Solid vinyl ether terminated urethane curing agent |
| US6291541B1 (en) * | 1997-12-16 | 2001-09-18 | Morton International Inc. | Solid vinyl ether terminated urethane curing agent |
| CN102010558A (en) * | 2010-10-11 | 2011-04-13 | 中国海洋石油总公司 | Acrylic acid non-aqueous dispersoid containing amino ester bonds and siloxy groups and preparation method thereof |
| WO2014173861A1 (en) * | 2013-04-26 | 2014-10-30 | Dsm Ip Assets B.V. | Vinyl functionalized urethane resins for powder coating compositions |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10543639B2 (en) | 2016-08-19 | 2020-01-28 | The Procter & Gamble Company | Method for manufacturing a three-dimensional object |
| US11529760B2 (en) | 2016-08-19 | 2022-12-20 | The Procter & Gamble Company | Polymeric materials and articles manufactured there from |
| CN110300637A (en) * | 2017-02-17 | 2019-10-01 | 巴斯夫欧洲公司 | Reactive thermoplastic polyurethane based on closed isocyanates |
| WO2019199482A1 (en) * | 2018-04-10 | 2019-10-17 | The Procter & Gamble Company | Polymeric materials and articles manufactured there from |
| CN111971031A (en) * | 2018-04-10 | 2020-11-20 | 宝洁公司 | Polymeric materials and articles made therefrom |
| US11723875B2 (en) | 2018-04-10 | 2023-08-15 | The Procter & Gamble Company | Polymeric materials and articles manufactured there from |
| CN108893088A (en) * | 2018-06-07 | 2018-11-27 | 太仓萃励新能源科技有限公司 | A kind of PTC function SPUR adhesive |
| CN113278125A (en) * | 2021-05-28 | 2021-08-20 | 南京玖泰新材料科技有限公司 | Photo-curing polyurethane and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105294986B (en) | 2018-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105294986A (en) | Solid-state hypocrystalline unsaturated polyurethane prepolymer and preparation method thereof | |
| CN103517946B (en) | Acrylic resin composition, acrylic resin sheet, acrylic resin duplexer and their manufacture method | |
| CN109562567A (en) | For manufacturing the method and composition to form three-dimension object by addition process | |
| CN101173032A (en) | Large-molecular weight polyurethane acrylic ester and synthesizing method thereof | |
| CN107690446B (en) | Hydrophobic polyols | |
| CN110093107A (en) | The manufacturing method of bonding sheet and its manufacturing method and image display device | |
| WO2014200452A2 (en) | Dispersion of a functionalized polyolefin in a polyol | |
| CN105143384A (en) | Pressure-sensitive adhesive composition and pressure-sensitive adhesive sheet using same | |
| CN107459959A (en) | A kind of flexible package adhesive for solvent-free use of resistance to boiling and preparation method thereof | |
| JP5698132B2 (en) | Resin composition maintaining lubricity when wet | |
| CN110093111A (en) | Bonding sheet and its manufacturing method and image display device | |
| CN102066517A (en) | Active-energy-ray-curable sealing agent composition, and member having sealing layer attached thereto | |
| AU2010304271B2 (en) | Coating material for hand application | |
| CN111748295A (en) | Asphalt-based waterproof coiled material and preparation method thereof | |
| CN111117548A (en) | Thermoplastic polyurethane adhesive and preparation thereof | |
| WO2018198899A1 (en) | Reactive hot melt adhesive | |
| US20130040868A1 (en) | Resin composition whose lubricity under wet conditions is maintained | |
| JP5667416B2 (en) | Laminated body | |
| CN117157341A (en) | Thermal interface material | |
| KR101104149B1 (en) | Method for manufacturing floor material comprising ethylene vinyl acetate and hydroxyacrylate and floor material made thereby | |
| JP2003064349A (en) | Polyurethane-based coating film waterproof material and construction method for coating film-waterproofing using the same | |
| CN106661409A (en) | Primer for adhesive tapes | |
| JP4232094B2 (en) | Composition for flexible resin molding excellent in high-temperature shear bonding performance and flexible resin molding obtained therefrom | |
| CN109837054A (en) | A kind of two component polyurethane adhesive and its preparation method and application | |
| EP3738772B1 (en) | Dual cure polyurethane formulations for 3d printing applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No.5 Lisha East Road, Shatian Town, Dongguan City, Guangdong Province 523000 Patentee after: Qingtian Material Technology Co., Ltd Address before: Shiling Town, Huadu District, Guangzhou City, Guangdong province 510860 Yufeng Road No. 16 Patentee before: GUANGZHOU KINTE INDUSTRIAL Co.,Ltd. |