CN106750114A - 6 degree of functionality waterborne polyurethane resins and preparation method and the waterborne polyurethane resin adhesive based on bipentaerythrite - Google Patents
6 degree of functionality waterborne polyurethane resins and preparation method and the waterborne polyurethane resin adhesive based on bipentaerythrite Download PDFInfo
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- CN106750114A CN106750114A CN201611033171.XA CN201611033171A CN106750114A CN 106750114 A CN106750114 A CN 106750114A CN 201611033171 A CN201611033171 A CN 201611033171A CN 106750114 A CN106750114 A CN 106750114A
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- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/30—Low-molecular-weight compounds
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6648—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6655—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3225 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
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- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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- C09J175/04—Polyurethanes
- C09J175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
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Abstract
The present invention relates to a kind of 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite and preparation method and the waterborne polyurethane resin adhesive, belong to polyurethanes technology field.Be incorporated into bipentaerythrite in aqueous polyurethane strand and serve as crosslinking points by the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite that the present invention is provided, enabling to molecule chain network space becomes narrower and small, pile up finer and close on space structure, and then the water resistance and weatherability of waterborne polyurethane resin can be improved.The preparation method of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite that the present invention is provided is prepared based on the degree of functionality waterborne polyurethane resin of bipentaerythrite six as raw material using poly- (carbonic ester ether) dihydroxylic alcohols, it is its important component that this kind of dihydroxylic alcohols has used carbon dioxide in preparation process, carbon emission is not only reduced, dependence of the polyurethane to fossil resources is decreased.The glue film performance as obtained in the waterborne polyurethane resin adhesive is good.
Description
Technical field
The present invention relates to polyurethanes technology field, and in particular to a kind of aqueous poly- ammonia of 6 degrees of functionality based on bipentaerythrite
Ester resin and preparation method and the waterborne polyurethane resin adhesive.
Background technology
The block polymer that polyurethane is made up of soft section and hard section.Soft section in polyurethane is by polymer polyatomic alcohol structure
Resistance to low temperature, elongation at break and elasticity into, there is provided polyurethane;Hard section is made up of isocyanates and small molecule chain extender,
Act as the crosslinking points of polyurethane, there is provided modulus, intensity and heat resistance etc..Different soft and hard segments combinations can assign polyurethane
Various excellent performances.However as the appearance of various countries' Environmental security laws and regulations, many countries have limited the poly- ammonia of solvent-borne type
The application of ester.The development of aqueous polyurethane is paid attention to production by countries in the world, and all achieves significant progress.
The aqueous polyurethane and traditional PEPA and PPG prepared using poly(carbonate-ether) polyol
The aqueous polyurethane of preparation, compared to having more excellent water resistance and mechanical performance, is a kind of ideal for preparing Aqueous Adhesives
Raw material.Yet with hydrophilic radical is introduced in the preparation of aqueous polyurethane, result in waterborne polyurethane resin water resistance,
Weatherability awaits further raising.
The content of the invention
The invention solves the problems that the technical problem of the water resistance of existing waterborne polyurethane resin, weatherability difference, there is provided Yi Zhongji
In the 6 degree of functionality waterborne polyurethane resins and preparation method and the waterborne polyurethane resin adhesive of bipentaerythrite.
In order to solve the above-mentioned technical problem, technical scheme is specific as follows:
A kind of 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite, its structure such as formula 1) shown in:
In formula, p is that 2-20, k are that 2-20, v are that 2-20, q are that 2-20, x are that 2-20, y are 2-20;
R1It is the one kind in following structure:
R2Structure such as formula 7) shown in:
Wherein, m is that 1~30, n is 1~35;
R3It is the one kind in following structure:
A kind of preparation method of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite, comprises the following steps:
(1), under nitrogen protection, by water removal after poly- (carbonic ester-ether) dihydroxylic alcohols and diisocyanate in organic solvent
Middle reaction, obtains the first product;
The diisocyanate is methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), the isocyanic acid of isophorone two
One or more in ester, hexamethylene diisocyanate and 4,4'- dicyclohexyl methyl hydride diisocyanates;
The organic solvent is the one kind in acetone, butanone, cyclohexanone;
(2), the first described product and hydrophilic chain extender are reacted in the presence of catalyst, the second product is obtained;
Described hydrophilic chain extender is N methyldiethanol amine;
Described catalyst is dibutyl tin laurate;
(3), the second described product and bipentaerythrite are reacted, third product is obtained;
(4), described third product and butanediol are reacted, after being neutralized with acid, adds deionized water to emulsify, solvent is evaporated off
Obtain the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite.
In the above-mentioned technical solutions, the molecular weight of poly- (carbonic ester-ether) dihydroxylic alcohols is 1500~5000 dalton.
In the above-mentioned technical solutions, the temperature reacted described in step (1) is 70~80 DEG C, and the time is 1.5~3 hours.
In the above-mentioned technical solutions, the temperature reacted described in step (2) is 30~40 DEG C, and the time is 1~2 hour.
In the above-mentioned technical solutions, the temperature reacted described in step (3) is 65~80 DEG C, and the time is 1.5~2 hours.
In the above-mentioned technical solutions, the temperature reacted described in step (4) is 65~80 DEG C, and the time is 1.5~2 hours.
In the above-mentioned technical solutions, the acid described in step (4) is in trifluoroacetic acid, trichloroacetic acid, acetic acid and hydrochloric acid
One kind.
A kind of 6 degree of functionality waterborne polyurethane resin adhesives based on bipentaerythrite, component and its weight portion are as follows:
In the above-mentioned technical solutions, the aqueous defoamer be BYK-019, BYK-020, BYK-024, BYK-028 or
BYK-1730;The aqueous dispersion is BYK-023, BYK-034, BYK-077, BYK-085, BYK-182 or BYK-190;Institute
Waterborne curing agent is stated for Desmodur DN, Bayhydur3100, Bayhydur2487/1, Bayhydur2457 or Bayhydur
2451。
The beneficial effects of the invention are as follows:
Bipentaerythrite is incorporated into water by the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite that the present invention is provided
Serve as crosslinking points in property polyurethane molecular chain, enable to molecule chain network space to become narrower and small, piled up on space structure
Obtain finer and close, and then the water resistance and weatherability of waterborne polyurethane resin can be improved.
The preparation method of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite that the present invention is provided is using poly-
(carbonic ester-ether) dihydroxylic alcohols is prepared as raw material and is based on the degree of functionality waterborne polyurethane resin of bipentaerythrite six, this kind of dihydroxylic alcohols
Use carbon dioxide for its important component in preparation process, not only reduced carbon emission, decrease polyurethane to petrochemical industry
The dependence of resource.By the use of bipentaerythrite as crosslinking agent, bipentaerythrite is incorporated into polyurethane molecular chain and is enabled to
Molecule chain network space diminishes, and piles up finer and close on space structure, and then can improve the water-fast of waterborne polyurethane resin
Property and weatherability.
With the present invention provide the 6 degree of functionality waterborne polyurethane resin adhesives based on bipentaerythrite obtained in glued membrane,
Glued membrane intensity 186N/2.5cm~215N/2.5cm, the peeling force after circulates is 147N/2.5cm~180N/
2.5cm, by after 4 high/low-temperature impacts of circulation, the test of damp and hot weatherability, glued membrane does not have any alice and comes unglued, peeling force
It is 116N/2.5cm~138N/2.5cm.
Brief description of the drawings
The present invention is described in further detail with reference to the accompanying drawings and detailed description.
Fig. 1 is the infrared spectrogram of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite prepared by embodiment 1.
Fig. 2 is the infrared spectrogram of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite prepared by embodiment 1.
Specific embodiment
The present invention is described in detail below in conjunction with the accompanying drawings.
The 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite that the present invention is provided, its structure such as formula 1) shown in:
In formula, p is that 2-20, k are that 2-20, v are that 2-20, q are that 2-20, x are that 2-20, y are 2-20;
R1It is the one kind in following structure:
R2Structure such as formula 7) shown in:
Wherein, m is 1~30, and preferably m is 10-25;N is 1~35, and preferably n is 5-30;
R3It is the one kind in following structure:
The preparation method of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite that the present invention is provided, specifically includes
Following steps:
(1) after, under nitrogen protection, poly- (carbonic ester-ether) dihydroxylic alcohols is removed water with diisocyanate in organic solvent
Reaction, obtains the first product;
(2), described the first product and hydrophilic chain extender N methyldiethanol amine are reacted under catalyst action, is obtained
Second product;
(3), the second described product and bipentaerythrite are reacted, third product is obtained;
(4), described third product and butanediol are reacted, after adding acid to neutralize, add deionized water emulsification, be evaporated off it is molten
Agent is to obtain the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite.
The source of poly- (carbonic ester-ether) dihydroxylic alcohols of the present invention for being used is simultaneously unrestricted, preferably according to patent
Prepared by 201210086834.X or method disclosed in patent 201110231493.6, its structure such as formula 7) shown in:
M is 1~30, preferably 10~25;N is 1~35, preferably 5~30.
The present invention will be with formula 7) after the water removal of poly- (carbonic ester-ether) dihydroxylic alcohols of structure, with diisocyanate organic molten
Reacted in agent, obtain the first product.The present invention is more excellent for the water removal mode and unrestricted, preferably vacuum distillation water removal
Elect as under the conditions of temperature is for 105~115 DEG C, vacuum distillation 50~80 minutes.
The present invention will be with formula 7) after the water removal of poly- (carbonic ester-ether) dihydroxylic alcohols of structure, add catalyst and two isocyanic acids
Ester reacts in organic solvent, obtains the first product.The catalyst is dibutyl tin laurate, and the diisocyanate is excellent
Selected from methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), isoflurane chalcone diisocyanate, hexamethylene diisocyanate with
And one or more in 4,4'- dicyclohexyl methyl hydride diisocyanate, more preferably toluene di-isocyanate(TDI), diphenyl methane
One kind in diisocyanate, hexamethylene diisocyanate and 4,4'- dicyclohexyl methyl hydride diisocyanates;The organic solvent
One kind preferably in butanone, acetone, cyclohexanone, more preferably butanone or acetone, most preferably butanone;The reaction temperature is excellent
Elect 70~80 DEG C as, the reaction time is 1.5~3 hours;
After obtaining the first product, to N methyldiethanol amine is added in the first product, the second product is obtained.The N- methyl
The feed postition of diethanol amine is preferably dropping funel dropwise addition, and N methyldiethanol amine is mixed in organic solvent, described to have
Machine solvent is preferably the one kind in butanone, acetone, cyclohexanone, more preferably butanone or acetone, most preferably butanone;Time for adding
It is controlled to 1h completion of dropping.The reaction temperature is preferably 30~40 DEG C, and the reaction time is preferably 1~2 hour.
After obtaining the second product, third product is obtained to bipentaerythrite is added in the second product.The reaction temperature is excellent
Elect 65~80 DEG C as, the reaction time is preferably 1.5~2 hours.
After obtaining third product, to adding butanediol to obtain the 4th product in third product, the reaction temperature is preferably
65~80 DEG C, the reaction time is preferably 1.5~2 hours.
It is 6~7 to obtain be added thereto to acid after the 4th product carrying out being neutralized to pH, described acid be preferably trifluoroacetic acid,
One kind in trichloroacetic acid, acetic acid and hydrochloric acid.Deionized water is subsequently adding, is stirred, the mixing speed is preferably 1200
~1800rpm, mixing time is preferably 0.5~2h, and solvent is then evaporated off, and to obtain 6 degrees of functionality based on bipentaerythrite aqueous
Polyurethane resin.The present invention is simultaneously unrestricted for the mode of the removing solvent, mode well known to those skilled in the art,
Preferably vacuum distillation.
Present invention also offers a kind of 6 degree of functionality waterborne polyurethane resin adhesives based on bipentaerythrite, component and
Its weight point is as follows:With formula 1) 108-180 parts of the 6 degree of functionality waterborne polyurethane resin based on bipentaerythrite of structure;Gas
0.78-2.90 parts of phase white carbon;Blanc fixe 21-35.5 parts;Aqueous defoamer 0.05-0.50 parts;Aqueous dispersion 0.06-
0.49 part;Waterborne curing agent 6.94-13 parts.
The aqueous dispersion is preferably BYK-023, BYK-034, BYK-077, BYK-085, BYK-182 or BYK-190,
More preferably BYK-034, BYK-085, BYK-182 or BYK-190;The aqueous defoamer be preferably BYK-019, BYK-020,
BYK-024, BYK-028 or BYK-1730, more preferably BYK-019, BYK-024, BYK-028 or BYK-1730;It is described aqueous
Curing agent is preferably DesmodurDN, Bayhydur3100, Bayhydur 2487/1, Bayhydur2547 or Bayhydur
2451, the more preferably one kind in Bayhydur3100, Bayhydur2457 or Bayhydur2451.
The present invention enters to glued membrane obtained in the 6 degree of functionality waterborne polyurethane resin adhesives based on bipentaerythrite that obtain
The performance test of row peeling force, detailed process is as follows:
The 6 degree of functionality waterborne polyurethane resin adhesives based on bipentaerythrite are sprayed on ABS plastic base material respectively
On automobile door protection panel and the polyurethane leather for posting non-woven fabrics, quantity for spray is 170~200g/cm2, then will be with based on double seasons
The automobile door protection panel of 6 degree of functionality waterborne polyurethane resin adhesive ABS plastic base materials of penta tetrol and with based on double Ji Wusi
6 degree of functionality waterborne polyurethane resin adhesives of alcohol post non-woven fabrics polyurethane leather respectively in an oven baking 30~
50s, is finally pasted the automobile door protection panel of ABS plastic base material with the polyurethane leather for posting non-woven fabrics, obtains being bonded sample
Part;After bonding exemplar room temperature is shelved into 72h, under 80% relative humidity, 80 DEG C are risen to from 30 DEG C, keep 4h;From at 80 DEG C
- 40 DEG C are dropped to, under 30% relative humidity, 4h is kept;25 DEG C are risen to from -40 DEG C, under relative humidity 30%, 1h is kept,
This process is a circulation, and the test of peeling force is carried out to glued membrane;After so carrying out 4 circulations, peeling force is carried out to glued membrane
Test.
Test result shows:Glued membrane intensity 186N/2.5cm~215N/2.5cm, be by the peeling force after a circulation
147N/2.5cm~180N/2.5cm, by after 4 high/low-temperature impacts of circulation, the test of damp and hot weatherability, glued membrane is not any
Alice and come unglued, peeling force is 116N/2.5cm~138N/2.5cm.
It is with reference to the embodiment content that the present invention is furture elucidated but of the invention in order to be better understood from the present invention
Content is not limited solely to the following examples.
Embodiment 1
Method according to patent 201210086834.X disclosed embodiments 9 prepares number-average molecular weight for 2000 dongles
Poly- (carbonic ester-ether) dihydroxylic alcohols for pausing.
Poly- (carbonic ester-ether) dihydroxylic alcohols that 185 grams of molecular weight for preparing are 2000 dalton is added in there-necked flask,
110 DEG C are heated to, are dehydrated 1 hour under -0.98MPa, be cooled to 75 DEG C, under nitrogen protection, add 86 grams of butanone and 90 grams
4,4'- dicyclohexyl methyl hydride diisocyanates react 2 hours, are then cooled to 38 DEG C, and 0.0023 gram of fourth of tin dilaurate two is added dropwise
Base tin catalyst, adds 11.40 grams of N methyldiethanol amines, addition to be reacted 1 hour after finishing in three batches, then heats to 65
DEG C, 5.80 grams of bipentaerythrites are added, react 1.5 hours, 6.7 grams of butanediols are subsequently adding, react 2 hours, add glacial acetic acid
PH is neutralized to 7,350 grams of deionized waters are subsequently adding, 1200rpm is stirred 1 hour, and butanone is removed under reduced pressure, that is, obtained based on double seasons
6 degree of functionality waterborne polyurethane resins of penta tetrol.
The 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite prepared to the embodiment of the present invention 1 carry out red
Outer detection, testing result is as shown in Figure 1:Fig. 1 is 6 degrees of functionality based on bipentaerythrite that the embodiment of the present invention 1 is prepared
The infrared spectrum of waterborne polyurethane resin:791cm-1,854cm-1,918cm-1,974cm-1,1074cm-1,1120cm-1,
1163cm-1,1250cm-1,1379cm-1,1461cm-1,1535cm-1,1749cm-1,2955cm-1,3340cm-1。
Embodiment 2
Method according to patent 201210086834.X disclosed embodiments 9 prepares number-average molecular weight for 2000 dongles
Poly- (carbonic ester-ether) dihydroxylic alcohols for pausing.
Poly- (carbonic ester-ether) dihydroxylic alcohols that 162 grams of molecular weight for preparing are 2000 dalton is added in there-necked flask,
Be heated to 110 DEG C, be dehydrated 1 hour under -0.98MPa, be cooled to 80 DEG C, under nitrogen protection, add 135 grams of butanone and
51.20 grams of toluene di-isocyanate(TDI)s react 2 hours, are then cooled to 32 DEG C, 0.0018 gram of dibutyl tin laurate is added dropwise and urges
Agent, adds 9.93 grams of N methyldiethanol amines, addition to be reacted 1 hour after finishing in three batches, then heats to 75 DEG C, adds
4.59 grams of bipentaerythrites, react 1.5 hours, are subsequently adding 5.82 grams of butanediols, react 2 hours, add in glacial acetic acid and pH
To 7,240 grams of deionized waters are subsequently adding, 1200rpm is stirred 1 hour, and butanone is removed under reduced pressure, that is, obtain based on bipentaerythrite
6 degree of functionality waterborne polyurethane resins.
The 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite prepared to the embodiment of the present invention 2 carry out red
Outer detection, testing result is as shown in Figure 2:Fig. 2 is 6 degrees of functionality based on bipentaerythrite that the embodiment of the present invention 2 is prepared
The infrared spectrum of waterborne polyurethane resin:792cm-1,855cm-1,919cm-1,975cm-1,1073cm-1,1121cm-1,
1164cm-1,1252cm-1,1378cm-1,1462cm-1,1536cm-1,1748cm-1,2956cm-1,3341cm-1。
Embodiment 3
Method according to patent 201210086834.X disclosed embodiments 11 prepares number-average molecular weight for 1500 roads
Poly- (carbonic ester-ether) dihydroxylic alcohols that you pause.
Poly- (carbonic ester-ether) dihydroxylic alcohols that 180 grams of molecular weight for preparing are 1500 dalton is added in there-necked flask,
Be heated to 110 DEG C, be dehydrated 1 hour under -0.98MPa, be cooled to 70 DEG C, under nitrogen protection, add 280 grams of butanone and
112.5 grams of methyl diphenylene diisocyanates react 1.5 hours, are then cooled to 35 DEG C, and 0.0030 gram of tin dilaurate two is added dropwise
Butyl tin catalyst, adds 14.56 grams of N methyldiethanol amines, addition to be reacted 2 hours after finishing in three batches, then heats to 70
DEG C, 6.73 grams of bipentaerythrites are added, react 2 hours, 8.75 grams of butanediols are subsequently adding, react 1.5 hours, add glacial acetic acid
PH is neutralized to 7,350 grams of deionized waters are subsequently adding, 1200rpm is stirred 1 hour, and butanone is removed under reduced pressure, that is, obtained based on double seasons
6 degree of functionality waterborne polyurethane resins of penta tetrol.
The 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite prepared to the embodiment of the present invention 3 carry out red
Outer detection, the infrared spectrum of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite that the embodiment of the present invention 3 is prepared
Testing result is:790cm-1,856cm-1,919cm-1,976cm-1,1076cm-1,1122cm-1,1165cm-1,1254cm-1,
1378cm-1,1460cm-1,1536cm-1,1750cm-1,2956cm-1,3341cm-1。
Embodiment 4
Method according to the disclosed embodiment 17 of patent 201110231493.6 prepares number-average molecular weight for 3500 roads
Poly- (carbonic ester-ether) dihydroxylic alcohols that you pause.
Poly- (carbonic ester-ether) dihydroxylic alcohols that 171 grams of molecular weight for preparing are 3500 dalton is added in there-necked flask,
110 DEG C are heated to, are dehydrated 1 hour under -0.98MPa, be cooled to 78 DEG C, under nitrogen protection, add 150 grams of butanone and 31 grams
1, hexamethylene-diisocyanate reacts 3 hours, is then cooled to 30 DEG C, and 0.0013 gram of dibutyltin dilaurate catalyst is added dropwise,
Add 6.00 grams of N methyldiethanol amines, addition to be reacted 1 hour after finishing in three batches, then heat to 80 DEG C, add 2.77 grams
Bipentaerythrite, reacts 1.5 hours, is subsequently adding 3.50 grams of butanediols, reacts 2 hours, with pH to 7 in addition glacial acetic acid, so
300 grams of deionized waters are added afterwards, and 1200rpm is stirred 1 hour, and butanone is removed under reduced pressure, that is, obtain 6 functions based on bipentaerythrite
Degree waterborne polyurethane resin.
The 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite prepared to the embodiment of the present invention 4 carry out red
Outer detection, the infrared spectrum of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite that the embodiment of the present invention 4 is prepared
Testing result is:789cm-1,852cm-1,920cm-1,976cm-1,1076cm-1,1122cm-1,1160cm-1,1248cm-1,
1378cm-1,1460cm-1,1538cm-1,1749cm-1,2956cm-1,3342cm-1。
Embodiment 5
Method according to patent 201210086834.X disclosed embodiments 8 prepares number-average molecular weight for 2800 dongles
Poly- (carbonic ester-ether) dihydroxylic alcohols for pausing.
Poly- (carbonic ester-ether) dihydroxylic alcohols that 198 grams of molecular weight for preparing are 2800 dalton is added in there-necked flask,
110 DEG C are heated to, are dehydrated 1 hour under -0.98MPa, be cooled to 74 DEG C, under nitrogen protection, add 250 grams of butanone and 45 grams
Toluene di-isocyanate(TDI) reacts 2 hours, is then cooled to 40 DEG C, and 0.0013 gram of dibutyltin dilaurate catalyst is added dropwise, point
Three batches of additions, 8.70 grams of N methyldiethanol amines, addition is reacted 1 hour after finishing, and then heats to 68 DEG C, adds 4.00 grams pairs
Pentaerythrite, reacts 1.5 hours, is subsequently adding 5.10 grams of butanediols, reacts 2 hours, with pH to 7 in addition glacial acetic acid, then
300 grams of deionized waters are added, 1200rpm is stirred 1 hour, and butanone is removed under reduced pressure, that is, obtain 6 degrees of functionality based on bipentaerythrite
Waterborne polyurethane resin.
The 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite prepared to the embodiment of the present invention 5 carry out red
Outer detection, the infrared spectrum of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite that the embodiment of the present invention 5 is prepared
Testing result is:793cm-1,856cm-1,920cm-1,976cm-1,1073cm-1,1122cm-1,1165cm-1,1254cm-1,
1378cm-1,1460cm-1,1536cm-1,1747cm-1,2956cm-1,3342cm-1。
Embodiment 6
Method according to patent 201210086834.X disclosed embodiments 4 prepares number-average molecular weight for 5000 dongles
Poly- (carbonic ester-ether) dihydroxylic alcohols for pausing.
Poly- (carbonic ester-ether) dihydroxylic alcohols that 216 grams of molecular weight for preparing are 5000 dalton is added in there-necked flask,
110 DEG C are heated to, are dehydrated 1 hour under -0.98MPa, be cooled to 72 DEG C, under nitrogen protection, add 300 grams of butanone and 35.1
Gram IPDI reacts 2 hours, is then cooled to 34 DEG C, be added dropwise 0.0020 gram it is dibutyltindilaurate catalyzed
Agent, adds 5.78 grams of N methyldiethanol amines, addition to be reacted 1 hour after finishing in three batches, then heats to 76 DEG C, adds 2.47
Gram bipentaerythrite, reacts 1.5 hours, is subsequently adding 3.44 grams of butanediols, reacts 2 hours, adds in glacial acetic acid and pH is to 7,
400 grams of deionized waters are subsequently adding, 1200rpm is stirred 1 hour, and butanone is removed under reduced pressure, that is, obtain 6 officials based on bipentaerythrite
Energy degree waterborne polyurethane resin.
The 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite prepared to the embodiment of the present invention 6 carry out red
Outer detection, the infrared spectrum of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite that the embodiment of the present invention 6 is prepared
Testing result is:793cm-1,856cm-1,919cm-1,975cm-1,1076cm-1,1122cm-1,1165cm-1,1251cm-1,
1378cm-1,1460cm-1,1536cm-1,1747cm-1,2957cm-1,3343cm-1。
Glacial acetic acid described in above-described embodiment may be replaced by trifluoroacetic acid, trichloroacetic acid or hydrochloric acid, not another here
One enumerates.
Comparative example 1, waterborne polyurethane resin synthesizes
Preparation method is same as Example 3, only by formula 1) polyvalent alcohol of structure changes poly adipate succinic acid ester into, and will be double
Pentaerythrite changes trimethylolpropane into.
Comparative example 2, waterborne polyurethane resin synthesizes
Preparation method is same as Example 4, only by formula 1) polyvalent alcohol of structure changes polycaprolactone polyol into, by double seasons
Penta tetrol changes trimethylolpropane into.
Comparative example 3, waterborne polyurethane resin synthesizes
Preparation method is same as Example 4, only by formula 1) polyvalent alcohol of structure changes polypropylene glycol into, by bipentaerythrite
Change trimethylolpropane into.
Embodiment 7
It is prepared by the 6 degree of functionality waterborne polyurethane resin adhesives based on bipentaerythrite
The 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite are added in sand mill, gas phase hard charcoal is added
Black, blanc fixe, aqueous defoamer and aqueous dispersion, carry out sand milling 3.5-7h, obtain the first component;Add aqueous solidified
Agent, is stirred 2~5 minutes with the speed of 2200-3000rpm, then with the strainer filtering of 200 mesh, is obtained based on bipentaerythrite
6 degree of functionality waterborne polyurethane resin adhesives, raw materials used Ju Ti Pei Fang as shown in table 1, the adhesive that will be prepared
It is designated as WAD1~WAD6, DB1-DB3.
The aqueous dispersion may be replaced by BYK-023, BYK-077 or BYK-190;The aqueous defoamer may be used also
To replace with BYK-019 or BYK-1730;The waterborne curing agent may be replaced by DesmodurDN or Bayhydur
2487/1;Here no longer enumerate.
Table 1 is based on 6 degree of functionality waterborne polyurethane resin glue of bipentaerythrite with the sample preparation of the embodiment of the present invention 1~6
The formula of glutinous agent
Table 2 is based on 6 degree of functionality waterborne polyurethane resin adhesive performance tests of bipentaerythrite
Obviously, above-described embodiment is only intended to clearly illustrate example, and not to the restriction of implementation method.It is right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need and unable to be exhaustive to all of implementation method.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (10)
1. a kind of 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite, it is characterised in that its structure such as formula 1) shown in:
In formula, p is that 2-20, k are that 2-20, v are that 2-20, q are that 2-20, x are that 2-20, y are 2-20;
R1It is the one kind in following structure:
R2Structure such as formula 7) shown in:
Wherein, m is that 1~30, n is 1~35;
R3It is the one kind in following structure:
2. the preparation method of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite described in a kind of claim 1, it is special
Levy and be, comprise the following steps:
(1), under nitrogen protection, by water removal after poly- (carbonic ester-ether) dihydroxylic alcohols and diisocyanate it is anti-in organic solvent
Should, obtain the first product;
The diisocyanate be methyl diphenylene diisocyanate, toluene di-isocyanate(TDI), isoflurane chalcone diisocyanate, 1,
One or more in hexamethylene-diisocyanate and 4,4'- dicyclohexyl methyl hydride diisocyanates;
The organic solvent is the one kind in acetone, butanone, cyclohexanone;
(2), the first described product and hydrophilic chain extender are reacted in the presence of catalyst, the second product is obtained;
Described hydrophilic chain extender is N methyldiethanol amine;
Described catalyst is dibutyl tin laurate;
(3), the second described product and bipentaerythrite are reacted, third product is obtained;
(4), described third product and butanediol are reacted, after being neutralized with acid, is added deionized water to emulsify, solvent is evaporated off is obtained final product
To the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite.
3. the preparation method of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite described in claim 2, its feature exists
In the molecular weight of poly- (carbonic ester-ether) dihydroxylic alcohols is 1500~5000 dalton.
4. the preparation method of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite described in Claims 2 or 3, it is special
Levy and be, the temperature reacted described in step (1) is 70~80 DEG C, the time is 1.5~3 hours.
5. the preparation method of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite described in Claims 2 or 3, it is special
Levy and be, the temperature reacted described in step (2) is 30~40 DEG C, the time is 1~2 hour.
6. the preparation method of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite described in Claims 2 or 3, it is special
Levy and be, the temperature reacted described in step (3) is 65~80 DEG C, the time is 1.5~2 hours.
7. the preparation method of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite described in Claims 2 or 3, it is special
Levy and be, the temperature reacted described in step (4) is 65~80 DEG C, the time is 1.5~2 hours.
8. the preparation method of the 6 degree of functionality waterborne polyurethane resins based on bipentaerythrite described in Claims 2 or 3, it is special
Levy and be, the acid described in step (4) is the one kind in trifluoroacetic acid, trichloroacetic acid, acetic acid and hydrochloric acid.
9. a kind of 6 degree of functionality waterborne polyurethane resin adhesives based on bipentaerythrite described in claim 1, its feature exists
In component and its weight portion are as follows:
10. the 6 degree of functionality waterborne polyurethane resin adhesives based on bipentaerythrite according to claim 9, its feature
It is that the aqueous defoamer is BYK-019, BYK-020, BYK-024, BYK-028 or BYK-1730;The aqueous dispersion
It is BYK-023, BYK-034, BYK-077, BYK-085, BYK-182 or BYK-190;The waterborne curing agent is Desmodur
DN, Bayhydur3100, Bayhydur 2487/1, Bayhydur 2457 or Bayhydur 2451.
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CN110452347A (en) * | 2019-07-10 | 2019-11-15 | 广东德美精细化工集团股份有限公司 | A kind of urethane intermediates and preparation method thereof with waterproof performance |
CN115028798A (en) * | 2022-06-28 | 2022-09-09 | 海洋化工研究院有限公司 | Modified isocyanate resin containing branched structure and preparation method and application thereof |
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