CN105294986B - A kind of solid-state semicrystalline unsaturated polyurethanes prepolymer and preparation method thereof - Google Patents
A kind of solid-state semicrystalline unsaturated polyurethanes prepolymer and preparation method thereof Download PDFInfo
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- CN105294986B CN105294986B CN201510715519.2A CN201510715519A CN105294986B CN 105294986 B CN105294986 B CN 105294986B CN 201510715519 A CN201510715519 A CN 201510715519A CN 105294986 B CN105294986 B CN 105294986B
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- 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
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- 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
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- 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 kind of solid-state semicrystalline unsaturated polyurethanes prepolymers and preparation method thereof, 50 DEG C 145 DEG C of the melting range of the polyurethane prepolymer, melt viscosity≤100mpa.s, range of number-average molecular weight is between 250 to 5000, degree of unsaturation is 0.3 6mmol/g, react being made by NCO/OH equivalent proportions 0.8 to 1.2 for reactive material for ether capped dose with unsaturated alcohol with alkane chain base dihydric alcohol, polyisocyanates.The prepolymer is the solid polyurethane prepolymer with 50 DEG C of 145 DEG C of melting ranges for meeting construction property requirement, it not only shows good stability during storage, also there is sufficiently low melt viscosity prepolymer and the resin Composition containing the prepolymer to be made to apply and obtain excellent levelability in substrate surface, the degree of unsaturation of effective compensation resin system in light heat solidification process.
Description
Technical field
The present invention relates to blocked polyurethane prepolymers fields and polyurethane prepolymer hypocrystalline immobilization field, and in particular to
Solid-state semicrystalline unsaturated polyurethanes prepolymer, while being related to the preparation method of the prepolymer.
Background technology
End-sealed type polyurethane prepolymer is seen in coating ingredients based on report at present, such as US5,155,154, US4,977,
201, US5,087,664, EP884341, EP 583377, US5,741,824, JP2003-268302, WO2008/049857,
WO2006/007273 and WO2011/069969 etc., but these polyurethane prepolymers exist with liquid or highly viscous state, are applicable in
Range is limited to adhesive, and the fields such as liquid coating are not suitable for the low sticky state processed under low temperature Warm status or solid-state system
Unsaturated light heat cure applications field.
Light heat cured powder paint is the environmental protection coating material for having broad mass market foreground, and light heat cured powder paint is with powder
State is coated to substrate surface, and by heated baking melting levelling film forming, finally crosslinking curing forms a film under ultraviolet light.It answers
Use up/base material of heat curable powder coating is usually temperature-sensitive material such as MDF planks and plastic rubber substrate, levelling is melted for heating
Temperature have stringent limitation, general heat treatment temperature≤150 DEG C.
3D printing material such as commercial thermoplastic polyurethane elastomer（TPU）Using Fused Deposition Modeling technique（FDM）Insatiable hunger
With polyurethane prepolymer material, the bond properties of moulding material determines the workability and FDM techniques of rapidoprint with ropiness
The performance of product.CN201410005541.3 obtains plasticity bullet in thermoplastic polyurethane elastomer using polyolefin, softening agent etc.
Property body, polyolefins includes maleic anhydride graft phenylethene-ethylene-butylene, Styrene copolymer（MA-g-SEBS）Deng as master
The elastomeric component wanted, but widely apply polyolefin as moulding material component, the ropiness of material when can lead to melting extrusion,
Filamentous apparent property and adhesion etc. are unsatisfactory.
Invention content
One of the objects of the present invention is to provide a kind of solid-state semicrystalline unsaturated polyurethanes prepolymers.The prepolymer is
Based on the perfect of the adaptability for developing polyurethane prepolymer application range, to the viscosity and stable storing of urethane composition system
Property, which is made, to be further improved, and that develops meets the solid polyurethane pre-polymerization with 50 DEG C of -145 DEG C of melting ranges of construction property requirement
Object not only shows good stability during storage, it may have sufficiently low melt viscosity makes prepolymer and contains
The resin Composition of the prepolymer is applied and obtains excellent levelability in substrate surface, effective compensation resin in light heat solidification process
The degree of unsaturation of system.
The second object of the present invention is to provide the preparation method of 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 pre-polymerization
Object, 50 DEG C -145 DEG C of the melting range of polyurethane prepolymer, melt viscosity≤100mpa.s, range of number-average molecular weight is 250 to 5000
Between, degree of unsaturation is 0.3-6mmol/g, with alkane chain base dihydric alcohol, ether capped dose of polyisocyanates and unsaturated alcohol to react
Substance carries out reaction by NCO/OH equivalent proportions 0.8 to 1.2 and is made.
Polyurethane prepolymer provided by the invention has 50 DEG C of -140 DEG C of melting ranges, is the hypocrystalline being stabilized below melting range
Water white transparency or milky solid matter.Preferably >=300 and≤4000, melt viscosity is excellent for the range of number-average molecular weight of the prepolymer
Choosing≤50mpa.s.The polyurethane prepolymer can be used for preparing comprising at least one acrylic resin such as unsaturated polyester (UP) acrylic acid
Resin and/or epoxy acrylic resin, and optionally other compositions and additive powder paint compositions, by substrate surface
One layer of coating composition heat treatment of coating realizes that fused coating levelling, light heat cure the coating composition layer and obtain one admittedly
Change coating.The prepolymer can also be applied to increasing material manufacturing process simultaneously, and polyurethane elastomer can be effectively improved after melting extrusion and is existed
The workabilities such as the bond properties of work progress and ropiness.
In reactive material of the present invention, the alkane chain base dihydric alcohol is at least the C with symmetrical structure2To C12Alkane chain base two
One kind in first alcohol, the polyisocyanates include at least hexamethylene diisocyanate, and ether capped dose of the unsaturated alcohol is
Monohydroxy end-capping reagent containing unsaturated double-bond.Above-mentioned reactive material is preferably reacted with NCO/OH equivalent proportions 0.9-1.1, more excellent
The NCO/OH equivalent proportions of choosing are 0.95-1.05.
C of the present invention with symmetrical structure2To C12Alkane chain base dihydric alcohol have C2To C12Symmetry carbochain,
Applicable alkane chain base dihydric alcohol includes but not limited to following compound：Ethylene glycol, diethylene glycol, 1,3 propylene glycol, 2- methyl-1s,
3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,4-butanediol, 1,5-PD, 1,6- hexylene glycol, Isosorbide-5-Nitrae-hexamethylene two
Methanol, 1,7- heptandiol, 1,8- ethohexadiol, 1,9- nonanediol, 1,10- decanediol, 1,11- undecane, 1,12- dodecane
Glycol etc..The alkane chain base dihydric alcohol of above-mentioned symmetrical structure, also can be in addition to participating in reaction with the pure form of monomer
Two kinds or more of monomer mixture form meets the needs of reaction.When two kinds of alkane chain base glycol monomers participate in reaction, monomer
Equivalents ratio range is preferably 0.5:1-3:1, more preferably ranging from 1:1-2:1.Three kinds or more of alkane chain base glycol monomer
When participating in above-mentioned reaction, preferred equivalents ratio is equivalent ratio dosage.
The form of mixtures of pure form using monomer or more different monomers combination participates in reaction and alkane chain base
The hydroxyl total amount that dihydric alcohol provides accounts for the equivalents ratio for all hydroxyls for participating in reaction system, to the polyurethane prepolymer of the present invention
Melting range adjustment have key effect.C in reaction system2-C12Alkane chain base dihydric alcohol dosage, equivalents ratio account for OH totality
Proportional region is no more than 60%, preferably more than 50%, more preferably no more than 30%.
Polyisocyanates of the present invention includes at least a kind of hexamethylene diisocyanate.It is known or available
The hexamethylene diisocyanate of any type form or its isomers may be used, including two isocyanide of monomeric hexamethylene
Acid esters（Monomer HDI）And polymeric hexamethylene diisocyanate.Polymeric hexamethylene diisocyanate such as six methylenes
Group diisocyanate tripolymer（PHDI）.Haplotype and/or the NCO equivalents ratios of polymeric hexamethylene diisocyanate account for
The NCO population proportions of reaction system are not less than 40% preferably not lower than 50%, are more preferably not less than 70%, particularly preferably
Not less than 80%.
The polyisocyanates also may include methyl diphenylene diisocyanate（MDI）And/or Toluene-2,4-diisocyanate, 4- diisocyanates
Ester（TDI）, it is known that or available any type form methyl diphenylene diisocyanate（MDI）, Toluene-2,4-diisocyanate, 4- bis- is different
Cyanate（TDI）Or its isomers may be used, including monomeric diphenylmethane diisocyanate（MDI）, haplotype first
Benzene -2,4- diisocyanate（TDI）, polymeric diphenylmethane diisocyanate（PMDI）With polymer-type Toluene-2,4-diisocyanate, 4-
Diisocyanate（PTDI）Deng.Available methyl diphenylene diisocyanate isomers includes 2,4- diphenylmethane diisocyanates
Ester, 4,4- methyl diphenylene diisocyanates, Toluene-2,4-diisocyanate, 6- diisocyanate and their corresponding oligomer and mixture.Such as
Methyl diphenylene diisocyanate in reaction（MDI）And Toluene-2,4-diisocyanate, 4- diisocyanate（TDI）When being used in mixed way, the NCO of the two
Equivalents ratio is 95/5-65/35, preferably 90/10-70/30, more preferably 85/15-75/25.
The methyl diphenylene diisocyanate（MDI）And/or Toluene-2,4-diisocyanate, 4- diisocyanate（TDI）Total yield ratio
The NCO overall equivalent ratios that example accounts for reaction system are no more than 60%, are preferably no more than 40%, more preferably less than 30%, especially
Preferably no more than 20%.
Prepare unsaturated polyurethanes prepolymer, it should at least use a kind of ether capped dose of unsaturated alcohol, including vinyl alcohol
Ethers end-capping reagent, allyl alcohol ethers end-capping reagent and acrylic alcohol ethers end-capping reagent etc., meet sealing end requirement includes hydroxyl
Butyl vinyl ether, cyclohexyl -1,4- dimethanol monovinyl ethers, glycol divinyl ether, polyethylene glycol mono vinyl ether, alkene
Propyl polyethylene glycol, ethylene glycol monoallyl ether etc., they, which can be used alone, to be used in combination.Make simultaneously
When with above-mentioned two classes end-capping reagent, the equivalents ratio of the two is 0.5:1-1.5:1, preferred range is 0.8:1-1.2:1.
The present invention adjusts product polyurethane prepolymer not by changing the usage ratio of unsaturated alcohol ethers end-capping reagent
Saturation degree is to meet various activity of curing reaction and realize all kinds of curing performances, but excessively high degree of unsaturation is easy induction and prepares
The reaction process of the prepolymer or the double bond of product process are unstable, and suitable polyurethane prepolymer degree of unsaturation is pre-polymerization
The degree of unsaturation of object is 0.3-6mmol/g.The OH total yield proportional regions that the total yield ratio of end-capping reagent accounts for reaction system are 5%-
95%, preferred range is 30-85%, and more preferable range is 50%-85%.
The preparation method of the solid-state semicrystalline unsaturated polyurethanes prepolymer of the present invention exists in catalyst and polymerization inhibitor
Under, polyisocyanates is reacted with the alkane chain base dihydric alcohol progress first stage, and range of reaction temperature is 30 DEG C -160 DEG C；The polyisocyanate
After cyanate and alkane chain base diol reaction are complete, the outlet temperature of first stage reaction is kept, it is ether capped that unsaturated alcohol is added
Agent carries out second stage reaction, and the OH functional groups of ether capped dose of unsaturated alcohol carry out anti-with the NCO functional groups of reaction system remnants
It answers, obtains solid-state semicrystalline unsaturated polyurethanes prepolymer.
In first stage reaction, the polyisocyanates enters symmetrical alkane chain base dihydric alcohol system, right in a manner of being added dropwise
Alkane chain base dihydric alcohol is claimed to enter polyisocyanates system and symmetrical alkane chain base dihydric alcohol and polyisocyanates room in a manner of being added dropwise
The technique that the three kinds of reactive modes that feed intake to heat up are all alternatively is blended in temperature.Ether capped dose of the unsaturated alcohol is with dropwise addition
Mode feeds intake.
The alternative synthetic catalyst for preparing polyurethane prepolymer includes Titanium series catalyst and organic tin catalyst etc., preferably
Catalyst be organic tin catalyst.The polymerization inhibitor is hydroquinone monomethyl ether.
Semicrystalline polyurethane prepolymer provided by the invention has 50 DEG C of -140 DEG C of melting ranges, is to be stabilized below melting range
Hypocrystalline water white transparency or milky solid matter, viscosity≤100mpa.s after melting, have be applied to FDM increasing material manufacturings
Potentiality, bond properties and the ropiness etc. that polyurethane elastomer can be effectively improved after melting extrusion in work progress apply
Work performance.Its as coating and adhesive composition component, under the conditions of heating or UV Light melting by and coating/viscous
It ties the other components reaction in the compositions such as agent and a solidify coating is provided, be used especially in light heat cured powder paint
Group in composition and 3D printing light heat curable resin composition is graded field.And due to the watery fusion of the prepolymer with it is low
Melt viscosity characteristic advantageously accounts for the problem of the watery fusion levelability of light heat cured powder paint coating, while as painting
Effective compensation component when film ultraviolet light/heat cure ensures solidification effect.
Specific implementation mode
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- methyl diphenylene diisocyanate monomers（MDI）, Bayer Bitterfeld GmbH, NCO content >=33.6%；
Toluene-2,4-diisocyanate, 4- diisocyanate（TDI）, Bayer Bitterfeld GmbH, NCO content >=47%；
Alkane chain base dihydric alcohol, catalyst, polymerization inhibitor are commercially available.
Comparative example 1
By the hexamethylene diisocyanate trimer of 75.1g（PHDI）With dibutyltin dilaurate catalyst 0.03g
The reaction kettle for leading to nitrogen with agitating paddle is added simultaneously, is to slowly warm up to 60 DEG C, temperature-rise period keeps leading to nitrogen and stirring shape
State.The hydroxy butyl vinyl ether of 48.9g is slowly added dropwise（HBVE）Into hexamethylene diisocyanate trimer, it was added dropwise program-controlled
It is more than 80 DEG C that rate of addition processed, which avoids temperature of reaction system, and the process that is added dropwise keeps leading to nitrogen and stirring；Hydroxyl butyl second is added dropwise
Alkene ether（HBVE）After be to slowly warm up to 100 DEG C -120 DEG C, insulating process keeps leading to nitrogen and stirring, heat preservation 1 ~ 2
It discharges after hour, the brittle substance 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
It keeps leading to nitrogen and stirring, by 84.1g hexamethylene diisocyanate monomers（HDI）, two fourth of tin dilaurate
The reaction kettle for leading to nitrogen with agitating paddle is added with 0.01g hydroquinone monomethyl ethers polymerization inhibitor in base tin catalyst 0.05g simultaneously,
60 DEG C are to slowly warm up to, 1, the 6- hexylene glycols of 29.5g are slowly added dropwise（1,6-HDO）, process control rate of addition is added dropwise and avoids instead
It is more than 80 DEG C to answer system temperature, is to slowly warm up to 120 DEG C, keeps the temperature 1-2 hours and completes first stage reaction；44.1g is slowly added dropwise
Glycol divinyl ether (EGVE) enter first stage reaction system, be added dropwise process control rate of addition avoid reaction system temperature
Degree is no more than 130 DEG C；It slowly heats up after glycol divinyl ether is added dropwise and keeps 150 DEG C ~ 160 DEG C of temperature, after keeping the temperature 1h
Discharging, the brittle substance of milky after room temperature cooling, melting range are 135-143 DEG C, melt viscosity≤50mpa.s, and prepolymer is unsaturated
Spend 3.17mmol/g, number-average molecular weight 316.
Embodiment 2
It keeps leading to nitrogen and stirring, by 67.3g hexamethylene diisocyanate monomers（HDI）, two fourth of tin dilaurate
The reaction kettle for leading to nitrogen with agitating paddle is added with 0.01g hydroquinone monomethyl ethers polymerization inhibitor in base tin catalyst 0.04g simultaneously,
60 DEG C are to slowly warm up to, is slowly added dropwise the ethylene glycol of 6.2g, process control rate of addition is added dropwise and avoids the temperature of reaction system from being more than
80 DEG C, 120 DEG C are to slowly warm up to, 1-2 hours is kept the temperature and completes first stage reaction；The ethylene glycol of 52.9g is slowly added dropwise
Ether (EGVE) enters first stage reaction system, and it is more than 125 DEG C that process control rate of addition, which is added dropwise, and avoids temperature of reaction system；Drop
It slowly heats up after adding glycol divinyl ether and keeps 125 DEG C ~ 130 DEG C of temperature, discharge after keeping the temperature 1h, it is white after room temperature cooling
The brittle substance of color, melting range are 115-118 DEG C, melt viscosity≤50mpa.s, prepolymer degree of unsaturation 4.74mmol/g, and number is divided equally
Son amount 315.
Embodiment 3
It keeps leading to nitrogen and stirring, by 108.1g hexamethylene diisocyanate monomers（HDI）, 40.3g 2,4- bis-
Methylenebis phenyl isocyanate monomer（2,4-MDI）, dibutyltin dilaurate catalyst 0.07g and 0.01g hydroquinone list
The reaction kettle for leading to nitrogen with agitating paddle is added in methyl ether polymerization inhibitor simultaneously, is to slowly warm up to 60 DEG C, the 1 of 12.2g is slowly added dropwise,
6- hexylene glycols (1.6-HDO), it is more than 80 DEG C that process control rate of addition, which is added dropwise, and avoids temperature of reaction system, is to slowly warm up to 120
DEG C, it keeps the temperature 1-2 hours and completes first stage reaction；The glycol divinyl ether (EGVE) that 123.8g is slowly added dropwise enters the first rank
Section reaction system, it is more than 125 DEG C that process control rate of addition, which is added dropwise, and avoids temperature of reaction system；It is complete that glycol divinyl ether is added dropwise
It slowly heats up after finishing and keeps 120 DEG C -125 DEG C of temperature, discharge after keeping the temperature 1h, the brittle substance of white, melting range are after room temperature cooling
104 ~ 106 DEG C, melt viscosity≤40mpa.s, prepolymer degree of unsaturation 5.12mmol/g, number-average molecular weight 387.
Embodiment 4
It keeps leading to nitrogen and stirring, by 135.2g hexamethylene diisocyanate monomers（HDI）, tin dilaurate two
Butyl tin catalyst 0.07g is added simultaneously with 0.01g hydroquinone monomethyl ethers polymerization inhibitor leads to reacting for nitrogen with agitating paddle
Kettle is warming up to 60 DEG C, after the blend of 1, the 6- hexylene glycols of 5.9g and the neopentyl glycol of 5.2g is slowly added dropwise, process control is added dropwise
It is more than 80 DEG C that rate of addition, which avoids temperature of reaction system, is to slowly warm up to 120 DEG C, keeps the temperature 1-2 hours and completes first stage reaction；
The glycol divinyl ether (EGVE) that 124.1g is slowly added dropwise enters first stage reaction system, and process control rate of addition is added dropwise
It is more than 125 DEG C to avoid temperature of reaction system；It slowly heats up after glycol divinyl ether is added dropwise and keeps temperature 120 DEG C -125
DEG C, it discharges after keeping the temperature 1h, the brittle substance of white after room temperature cooling, 83 ~ 86 DEG C of melting range, melt viscosity≤50mpa.s, prepolymer is not
Saturation degree 5.21mmol/g, number-average molecular weight 336.
Embodiment 5
It keeps leading to nitrogen and stirring, by 100.9g hexamethylene diisocyanate monomers（HDI）, 37.5g hexichol
Dicyclohexylmethane diisocyanate（MDI）, 8.7g Toluene-2,4-diisocyanate, 4- diisocyanate（TDI）, dibutyltin dilaurate catalyst
The reaction kettle for leading to nitrogen with agitating paddle is added with 0.01g hydroquinone monomethyl ethers polymerization inhibitor in 0.07g simultaneously, is to slowly warm up to
60 DEG C, 1, the 6- hexylene glycols of 11.9g are slowly added dropwise, it is more than 80 DEG C that process control rate of addition, which is added dropwise, and avoids temperature of reaction system,
120 DEG C are to slowly warm up to, 1-2 hours is kept the temperature and completes first stage reaction；The glycol divinyl ether of 123.3g is slowly added dropwise
(EGVE) enter first stage reaction system, it is more than 125 DEG C that process control rate of addition, which is added dropwise, and avoids temperature of reaction system；It is added dropwise
It slowly heats up after glycol divinyl ether and keeps 120 DEG C -125 DEG C of temperature, discharge after keeping the temperature 1h, white after room temperature cooling
Brittle substance, melting range are 75 ~ 78 DEG C, melt viscosity≤40mpa.s, prepolymer degree of unsaturation 4.95mmol/g, molecular weight 403.
Embodiment 6
It keeps leading to nitrogen and stirring, by 67.3g hexamethylene diisocyanate monomers（HDI）, two fourth of tin dilaurate
The reaction kettle for leading to nitrogen with agitating paddle is added with 0.01g hydroquinone monomethyl ethers polymerization inhibitor in base tin catalyst 0.04g simultaneously,
60 DEG C are to slowly warm up to, the ethylene glycol of 6.2g is slowly added dropwise（EG）, process control rate of addition is added dropwise and avoids temperature of reaction system
More than 80 DEG C, 120 DEG C are to slowly warm up to, 1-2 hours is kept the temperature and completes first stage reaction；The ethylene that 31.8g is added dropwise is slowly added dropwise
Ethyl glycol ether (EGVE) and 24.6g ethylene glycol monoallyl ethers（EGAE）Into first stage reaction system, it was added dropwise program-controlled
It is more than 120 DEG C that rate of addition processed, which avoids temperature of reaction system,；It slowly heats up after glycol divinyl ether is added dropwise and keeps temperature
120 DEG C ~ 125 DEG C of degree discharges after keeping the temperature 1h, and the brittle substance of white after room temperature cooling, melting range is 96 ~ 98 DEG C, and melt viscosity≤
50mpa.s, prepolymer degree of unsaturation 4.62mmol/g, relative molecular weight 324.
Comparative example 2
It with blender, thermometer and is being connected in the four-hole bottle of nitrogen, 1000g is had into 30-35mgKOH/g acid values
Terminal carboxyl polyester resin（Guangzhou Kinte Material Technology Co., Ltd.）230 DEG C of heat preservations are heated to, are cooled down after resin melting completely
To 3g amines catalysts are added at 190 DEG C, continue after being cooled to 170 DEG C ~ 180 DEG C, the contracting of 90.6g methacrylic acids is slowly added dropwise
Water glyceride（GMA, chemistry is pure, commercially available, adds 0.03% polymerization inhibitor）.GMA be added dropwise after in 180-185 DEG C keep the temperature 30min after
Discharging, the viscosity for obtaining the polyester acrylate with double bond are 22000mpa s（140℃）, 1200 mpa s（200℃）.Iodine
The degree of unsaturation that amount method measures product is 0.52mmol/g.
Comparative example 3
It with blender, thermometer and is being connected in the four-hole bottle of nitrogen, 600g is had into 450-500g/eq epoxide equivalents
Epoxy resin（Guangzhou Hong Chang Electron Material Co., Ltd）It is heated to 150 DEG C of heat preservations, resin jointly with 1.2g amines catalysts
After being cooled to 110-115 DEG C after melting completely, 89.5g is slowly added dropwise（Methyl）Acrylic acid（Chemistry is pure, commercially available, addition 0.02%
Polymerization inhibitor）.It is more than 130 DEG C that control rate of addition, which avoids temperature,（Methyl）Acrylic acid is kept the temperature after being added dropwise in 120-125 DEG C
It discharges after 30min, the viscosity for obtaining undersaturated epoxy acrylate is 650 mpa s（140℃）, 430 mpa s（200
℃）.The degree of unsaturation that iodimetric titration measures product is 1.37mmol/g.
Experimental example
Evaluate effect of the solid-state semicrystalline unsaturated polyurethanes prepolymer in light heat cured powder paint, according to the form below
Component is weighed, is squeezed out through extruder mixing after mixing precomminution, extrudate obtains photocuring powder through pulverizer grinding and sieving again
Last coating.Coating is sprayed on the aluminium sheet through the oil removing that derusts using tribo-gun.
Using 2 resin of comparative example and 3 resin of comparative example as the matrix resin part of light heat cured powder paint, it is added half
Crystal type solid-state unsaturated polyurethanes prepolymer, in conjunction with including initiator, levelling agent, pigment, condiment, styrax composition light heat
Cured powder paint.
Powder coating component includes：Photoinitiator, Irgacure 184D, BASF；Thermal initiator, Trigonox BPIC-
C75, AKZO NOBEL；Levelling agent, Rheoflow PLP-100, KS CNT；Titanium dioxide, barium sulfate, styrax are commercially available.
The solidification of photocuring powdery paints, coated aluminium sheet, which is placed in, to be set as toasting 10min in 140 DEG C of Electric heat oven
Afterwards, coating is subjected to photocuring（UV energy 1500mJ/cm2）, coating after photocuring cooling available film at room temperature
Sample, for carrying out film performance test.
The solidification of heat curable powder coating, coated aluminium sheet, which is placed in, is set as baking-curing in 140 DEG C of Electric heat oven
It is cooling at room temperature to can get film sample after 10min, for carrying out film performance test.
The measurement of the bottom horizontal flow sheet of light heat cured powder paint
The melting levelability of the bottom horizontal flow sheet reflection coating of powdery paints, is that the correlation of the apparent flatness of film refers to
Mark.
Light heat cured powder paint is configured by a certain percentage, takes the powdery paints tabletting of 1g（A diameter of 15mm）After demould.
Thin discs will be obtained（Diameter 15mm）It is placed in the heating plate for being set temperature, waits for that thin discs constantly expand（Melting）10min
Afterwards, widened disc diameter d is measured with compasses, diameter d is bottom horizontal flow sheet, unit mm.
Solid-state semicrystalline unsaturated polyurethanes prepolymer is evaluated in fusion sediment increasing material manufacturing technique（FDM）Change in technology
Kind thermoplastic polyurethane elastomer（TPU）The ropiness of moulding material can be with the effect of adhesiveness.According to the form below configures moulding material
Composition uses fusion sediment type 3D printing equipment printed material, is scanned between cooperation UV layer, solidification is cold after melting extrusion wire drawing
But finished product is obtained afterwards, is tested for the property.
Moulding material component includes：Polyurethane elastomer 1, Kraton G series, Kraton Performance
Polymers Inc；Polyurethane elastomer 2, Tafmer series, Mitsui Chemicals；Polyolefin, PPC polypropylene series, Total
S.A；Photoinitiator, Irgacure 184D, BASF；Softening agent, Hydrobrite, Sonneborn Inc；Lubricant,
Kemamide series, PMC；Antioxidant, phosphorous acid esters are commercially available.
Fused Deposition Modeling（FDM）The ropiness of moulding material is evaluated, and will be squeezed out by 3D printer after material molten, even
Continuous to squeeze out 10 hours, statistics blocks the number of print head or fracture of wire, and number is as the index for judging moulding material ropiness.
From the result of above-mentioned experiment as it can be seen that the coating material solidified formula of the light heat for comparing not used prepolymer, has used this hair
The bottom horizontal flow sheet that the light heat of bright prepolymer is coating material solidified is significantly improved, and corresponding film performance is also improved；It can be seen that
The watery fusion of prepolymer and low melting viscosity characteristic, solve the watery fusion levelability of light heat cured powder paint coating
Problem.And since prepolymer provided by the invention is solid, light heat cured powder paint is not susceptible to during storage
Conglomeration.In addition, be added to the bond properties in work progress for effectively improving polyurethane elastomer of prepolymer of the present invention with
The workabilities such as ropiness.
Claims (4)
1. a kind of solid-state semicrystalline unsaturated polyurethanes prepolymer applied to increasing material manufacturing material, characterized in that the poly- ammonia
50 DEG C -145 DEG C of the melting range of ester prepolymer, melt viscosity≤50mpa.s, range of number-average molecular weight are >=300 and≤4000, insatiable hunger
It is 0.3-6mmol/g with degree, NCO/ is pressed for reactive material with alkane chain base dihydric alcohol, polyisocyanates and ether capped dose of unsaturated alcohol
OH equivalent proportions 0.9 to 1.1 carry out reaction and are made, wherein the alkane chain base dihydric alcohol is 1,4-CHDM, it is described
Polyisocyanates be monomeric hexamethylene diisocyanate and/or polymeric hexamethylene diisocyanate, it is described not
Ether capped dose of saturated alcohols include one or both of allyl polyglycol and ethylene glycol monoallyl ether for allyl alcohol ether
Combination.
2. the solid-state semicrystalline unsaturated polyurethanes prepolymer according to claim 1 applied to increasing material manufacturing material,
It is characterized in that the equivalents ratio of the alkane chain base dihydric alcohol, which accounts for OH population proportion ranges, is no more than 60%；The haplotype and/or
The NCO equivalents ratios of polymeric hexamethylene diisocyanate account for NCO population proportions and are ranging from not less than 40%；Unsaturated alcohol
The OH total yield proportional regions that ether capped dose of total yield ratio accounts for reaction system are 5%-100%.
3. the solid-state semicrystalline unsaturated polyurethanes prepolymer as claimed in claim 1 or 2 applied to increasing material manufacturing material
Preparation method, characterized in that in the presence of catalyst and polymerization inhibitor, polyisocyanates carries out the first stage with alkane chain base dihydric alcohol
Reaction, range of reaction temperature is 30 DEG C -160 DEG C；After the polyisocyanates and alkane chain base diol reaction are complete, first is kept
Ether capped dose of progress second stage reaction of unsaturated alcohol, the OH that ether capped dose of unsaturated alcohol is added in the outlet temperature of elementary reaction
Functional group is reacted with the NCO functional groups of reaction system remnants, obtains solid-state semicrystalline unsaturated polyurethanes prepolymer.
4. the solid-state semicrystalline unsaturated polyurethanes prepolymer according to claim 3 applied to increasing material manufacturing material
Preparation method, characterized in that the reactive mode that feeds intake of the first stage reaction is the polyisocyanates in a manner of being added dropwise
Enter polyisocyanates system or symmetrical in a manner of being added dropwise into symmetrical alkane chain base dihydric alcohol system, symmetrical alkane chain base dihydric alcohol
Heating is blended with polyisocyanates room temperature in alkane chain base dihydric alcohol；Ether capped dose of the unsaturated alcohol is fed intake in a manner of dropwise addition.
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| CN109640926A (en) | 2016-08-19 | 2019-04-16 | 宝洁公司 | Polymer material and the product being made from it |
| EP3582923B1 (en) * | 2017-02-17 | 2024-04-10 | Basf Se | Reactive thermoplastic polyurethane based on blocked isocyanates |
| 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 |
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| 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 |
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| 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 |
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