CN110028629A - A kind of preparation method for the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves - Google Patents
A kind of preparation method for the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves Download PDFInfo
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- CN110028629A CN110028629A CN201910347336.8A CN201910347336A CN110028629A CN 110028629 A CN110028629 A CN 110028629A CN 201910347336 A CN201910347336 A CN 201910347336A CN 110028629 A CN110028629 A CN 110028629A
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- alkenyl
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 75
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- -1 alkenyl acrylic ester Chemical class 0.000 title claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 29
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 27
- 230000004048 modification Effects 0.000 claims abstract description 25
- 238000012986 modification Methods 0.000 claims abstract description 25
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 22
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000839 emulsion Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims abstract description 13
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims abstract description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 20
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- PDSNLYSELAIEBU-UHFFFAOYSA-N Longifolene Chemical compound C1CCC(C)(C)C2C3CCC2C1(C)C3=C PDSNLYSELAIEBU-UHFFFAOYSA-N 0.000 claims description 11
- ZPUKHRHPJKNORC-UHFFFAOYSA-N Longifolene Natural products CC1(C)CCCC2(C)C3CCC1(C3)C2=C ZPUKHRHPJKNORC-UHFFFAOYSA-N 0.000 claims description 11
- 239000003112 inhibitor Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 230000006837 decompression Effects 0.000 claims description 3
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical group O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- 241000510678 Falcaria vulgaris Species 0.000 claims 3
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 239000002932 luster Substances 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 9
- 239000000853 adhesive Substances 0.000 abstract description 5
- 230000001070 adhesive effect Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 238000001723 curing Methods 0.000 description 10
- 238000010521 absorption reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000000016 photochemical curing Methods 0.000 description 5
- 238000012797 qualification Methods 0.000 description 5
- 230000002087 whitening effect Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229920006264 polyurethane film Polymers 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000012855 volatile organic compound Substances 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- GNEPLYVYORHREW-UHFFFAOYSA-N 1,1,3,3,6-pentamethyl-7-nitro-2h-inden-5-amine Chemical compound CC1=C(N)C=C2C(C)(C)CC(C)(C)C2=C1[N+]([O-])=O GNEPLYVYORHREW-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229940119545 isobornyl methacrylate Drugs 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-N phosphoric acid;yttrium(3+) Chemical compound [Y+3].OP(O)(O)=O UXBZSSBXGPYSIL-UHFFFAOYSA-N 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011527 polyurethane coating Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 125000001443 terpenyl group Chemical group 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229940113165 trimethylolpropane Drugs 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a kind of preparation methods of alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves, after aqueous polyurethane, come into leaves alkenyl modification acrylate, methacrylic acid, curing agent and trimethylol-propane trimethacrylate are stirred to react, initiator is added, modified aqueous polyurethane emulsion is made, modified aqueous polyurethane emulsion is formed into Green High Performance aqueous polyurethane by ultraviolet light.The present invention comes into leaves the preparation method of alkenyl acrylic ester modified water-soluble polyurethane, step is few, easy to operate, products obtained therefrom has good heat resistance, water resistance, mechanical property, hardness and solvent resistance, and bright luster is good, adhesive force is good, pencil hardness reaches 2H, and tensile strength reaches 27.22Mpa, and Tg is up to 34.3 DEG C, water resistance is qualified, VOC free release.
Description
Technical field
The present invention relates to a kind of preparation methods of alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves, and belong to aqueous polyurethane
Modification field.
Background technique
Attention due to various countries to the limitation of volatile organic compounds (VOC) discharge amount and to environmental protection, aqueous poly- ammonia
Ester (WPU), which is just gradually substituting solvent borne polyurethane in various fields, becomes the mainstream of polyurethane industries among others, such as coating, adhesive, spinning
It knits and many industrial circles such as leather processing.Most of aqueous polyurethane there are still solid contents low, glue film water resistance, hardness,
The disadvantages of glossiness is bad is used with certain limitation.
In order to expand WPU emulsion applications range, need to be modified it.Modified method mainly from it is organic-silicon-modified,
Epoxy resin modification, polyacrylate modified and organic fluorine richness etc..But these modified feedstocks are greatly mostly from fossil resources.In
State patent document CN109439166A discloses a kind of aqueous polyurethane coating, and galapectite powder and xenotime powder is taken to be uniformly mixed,
Hydrochloric acid, aniline is added, ultrasonic disperse adds ammonium persulfate, is stirred to react, and it filters, then obtained filter cake is washed,
Dry, grinding obtains modified galapectite powder；Finally galapectite powder is added in aqueous polyurethane, with excellent corrosion-resistant
Property, but its film forming speed and mechanical property are to be improved.Chinese patent literature CN108752535A discloses a kind of isobornyl thiocyanoacetate
The preparation method of modified photocuring aqueous polyurethane, obtained waterborne polyurethane glass transition temperature are promoted not enough, are stretched strong
Degree enhances unobvious.
Summary of the invention
In order to solve, small aqueous polyurethane emulsion hardness of the existing technology, heat-resisting, poor water resistance, form a film slow, mechanics
The bad disadvantage of performance, the present invention provide a kind of preparation method of acrylate modified photocuring aqueous polyurethane of the alkenyl that comes into leaves,
The aqueous polyurethane emulsion of preparation is high with glass transition temperature, tensile strength is big, fast, the heat-resisting water-tolerant of film forming, resistance toization
Learn the features such as agents good.
In order to solve the above technical problems, the technical solution adopted in the present invention is as follows:
A kind of preparation method for the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves, aqueous polyurethane, the alkenyl that comes into leaves are changed
Property acrylate, methacrylic acid, curing agent and trimethylol-propane trimethacrylate be stirred to react after, be added cause
Modified aqueous polyurethane emulsion is made in agent, and modified aqueous polyurethane emulsion is formed green by ultraviolet light
High-performance water-based polyurethane.
Applicant it has been investigated that, initiator will be individually added into finally, if solidification can be improved by being added jointly with monomer
Time simultaneously reduces material property.
In above-mentioned reaction process, generated without any toxic gas.
Applicant it has been investigated that, have a C=C double bond in the molecule for the alkenyl modification acrylate that comes into leaves, can use
Polyaddition reaction synthesizes different acrylate, these monomers are applied to adhesive, special type as photocureable coating diluent
Coating etc. has high activity, high rigidity, and the bridged cycloalkyl structure with terpenoid, imparts the special reason of the material
Change property, such as the good good characteristic of low viscosity, high glass transition temperature, low coloration, high refractive index, hydrophobicity；Longifolene simultaneously
Base acrylate may be used as photo-curing material, can be organically combined with aqueous polyurethane, solid as a kind of novel light
Change aqueous polyurethane, additionally by amine curing agent is added, finally accelerates film formation time, improve the heat-resisting of aqueous polyurethane
Property, water resistance and mechanical property, finally obtain the aqueous polyurethane haveing excellent performance.
Compared with fossil resources, biomass resource abundance, while there is renewable, cheap and biocompatibility
The advantages that, the application is modified WPU using the alkenyl esters of acrylic acid that comes into leaves, and is solidified with ultraviolet light, prepare low cost,
The aqueous polyurethane of function admirable.
The above-mentioned alkenyl acrylate that comes into leaves the preparation method comprises the following steps: acrylic acid and longifolene are mixed, polymerization inhibitor is added and urged
Agent reaction collects 113~120 DEG C of fraction, as come into leaves alkenyl modification acrylate after reaction at 0.6kPa；
Wherein, the quality dosage of longifolene is 1.8~2.5 times of acrylic acid quality, and the quality dosage of polymerization inhibitor is acrylic acid quality
0.8~1.2%, the quality dosage of catalyst is the 2.8~3.6% of acrylic acid quality.
In order to improve the purity for the alkenyl acrylate that comes into leaves, it is preferable that the alkenyl acrylate that comes into leaves the preparation method comprises the following steps: by third
Olefin(e) acid and longifolene mix, and polymerization inhibitor and catalyst is then added, and 16~18h is reacted under conditions of temperature is 55~65 DEG C,
Catalyst is filtered out, 0.8~1.2% polymerization inhibitor that quality dosage is acrylic acid quality is added, is steamed under decompression unreacted
Longifolene and acrylic acid, and 113~120 DEG C of fraction is collected at 0.6kPa, as come into leaves alkenyl modification acrylate.
In order to ensure product purity and reaction efficiency, it is preferable that polymerization inhibitor is phenthazine, and catalyst is phosphotungstic acid.
It is preferred that the preparation method of the above-mentioned alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves, will come into leaves alkenyl modified propylene
Acid esters, methacrylic acid, curing agent and trimethylol-propane trimethacrylate mixed liquor instill in aqueous polyurethane, drop
After adding, high-speed stirred 1-1.5 hours, initiator is then added, modified aqueous polyurethane emulsion is made, then passes through
Ultraviolet light forms Green High Performance aqueous polyurethane.
In order to improve the uniformity of reaction, to improve the performance of product, come into leaves alkenyl modification acrylate, metering system
The mixed liquor of acid, curing agent and trimethylol-propane trimethacrylate drips off in 30-40 minutes；High-speed stirred speed is
450-550r/min。
In order to ensure the comprehensive performance of product, it is preferable that the quality dosage of initiator be come into leaves alkenyl modification acrylate and
The 0.2~0.5% of methacrylic acid quality sum；The quality dosage of trimethylol-propane trimethacrylate changes for the alkenyl that comes into leaves
The 1~2% of property acrylate and methacrylic acid quality sum；The quality dosage of curing agent be come into leaves alkenyl modification acrylate and
The 2~3% of methacrylic acid quality sum；The mass ratio of alkenyl modification acrylate and methacrylic acid of coming into leaves is (1~3): 10,
Preferably 1:5；The quality of methacrylic acid is the 14-18% of aqueous polyurethane quality.
Aqueous polyurethane solid content used herein is 20-30%.It is preferred that aqueous polyurethane is there is grace chemical industry in Anhui
The production of limit company.The solid content of modified aqueous polyurethane emulsion is 30~40wt%.
Green High Performance aqueous polyurethane surface drying time is lower than 3 seconds.Namely surface layer moment is i.e. dry.
Initiator is photoinitiator, in order to promote the collaboration between each component to promote effect, further increases the power of product
Performance is learned, further preferably, photoinitiator is 2- hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -1- acetone.
In order to improve the heat resistance, water resistance and mechanical property of aqueous polyurethane, the collaboration between promotion each component promotes,
Curing agent be 1,2,3,4,5,6,7,8- octahydro -2,2- dimethyl -1,3- endo-methylene group azophenlyene, 1,2,3,4,5,6,7,8,8 α,
10 α-decahydro -2,2- dimethyl -1,3- endo-methylene group azophenlyene and 5,6,7,8- tetrahydro -4- (4'- aminomethyl phenyl) -7,7- diformazan
At least one of base -6,8- methylene bridge -2- quinazoline amine.
In order to further increase the tensile strength of product, ultraviolet lamp irradiation power is 100-200w, and the ultraviolet lighting time is
30 seconds to 2 minutes.
The unmentioned technology of the present invention is referring to the prior art.
The present invention comes into leaves the preparation method of alkenyl acrylic ester modified water-soluble polyurethane, and step is few, and easy to operate, gained produces
Product have good heat resistance, water resistance, mechanical property, hardness and solvent resistance, and bright luster is good, and adhesive force is good, and pencil is hard
Degree reaches 2H, and tensile strength reaches 27.22Mpa, and for Tg up to 34.3 DEG C, water resistance is qualified, VOC free release.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
In following embodiment, properties of product detection method are as follows: bright luster is measured using GB/T1743-1979；Adhesive force
It is measured using GB/T1720-1979；Tensile strength and elongation at break are measured using GB/T528-1992；Water absorption rate uses GB/T
1034-2008 measurement；Flexibility is measured using GB/T1731-1979；Heat analysis is measured using DSC differential scanning calorimeter, is used
The heat resistance of glass transition temperature Tg characterization aqueous polyurethane emulsion；Chemical reagent resistance is measured using GB 1763-1979.
Aqueous polyurethane in each example is purchased from Anhui Zhong En Chemical Co., Ltd., solid content 20-30%, model PU-
108。
Embodiment 1
It comes into leaves the preparation of alkenyl modification acrylate: acrylic acid 9.36g and longifolene 20.4g being pre-mixed, in room temperature
Lower dissolution is added in the four-hole boiling flask equipped with thermometer, condenser and mechanical agitator until completely dissolved, polymerization inhibitor is then added
Agent phenthazine 0.09g and phosphate-tungstic acid 0.3g, 60 DEG C of reaction 18h stop reaction, and catalyst, which is recovered by filtration, must react thick
Liquid.0.09g polymerization inhibitor phenthazine is added into filtered reaction solution, and unreacted longifolene and acrylic acid are steamed under decompression,
And 113~120 DEG C of fraction is collected at 0.6kPa, as come into leaves alkenyl modification acrylate.
Embodiment 2
Aqueous polyurethane 30.0g is slowly dropped into 5,6,7,8- tetrahydro -4- of curing agent under the conditions of stirring (500r/min)
(4'- aminomethyl phenyl) -7,7- dimethyl -6,8- methylene bridge -2- quinazoline amine 0.15g, come into leaves alkenyl modification acrylate
The mixed liquor (dripping off for 30 minutes) of 0.5g, trimethylol-propane trimethacrylate 0.08g and methacrylic acid 5g,
1h is reacted under the mixing speed of 500r/min, and initiator 2- hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) benzene is then added
Base] -1- acetone 0.02g, then product is layered in polyfluortetraethylene plate and is made aqueous within 2 minutes by ultraviolet lamp (100w) irradiation
Polyurethane film.Film layer surface drying time is lower than 3 seconds.
The bright luster 121 of product, adhesion 1 grade, tensile strength 25.33MPa, flexibility 1.5mm, Tg 30.8
DEG C, pencil hardness 2H, water absorption rate 39%, solvent resistance qualification (10%NaOH, non-whitening), modified aqueous polyurethane cream
Liquid (product before illumination) has good stability (be stored at room temperature 6 months not stratified).
Embodiment 3
Aqueous polyurethane 30.0g is slowly added to 5,6,7,8- tetrahydro -4- of curing agent under the conditions of stirring (500r/min)
(4'- aminomethyl phenyl) -7,7- dimethyl -6,8- methylene bridge -2- quinazoline amine 0.15g, come into leaves alkenyl modification acrylate
The mixed liquor (dripping off for 30 minutes) of 1.5g, trimethylol-propane trimethacrylate 0.08g and methacrylic acid 5g,
1h is reacted under the mixing speed of 500r/min, and initiator 2- hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) benzene is then added
Base] -1- acetone 0.02g, then product is layered in polyfluortetraethylene plate by 2 minutes obtained aqueous polyurethanes of ultraviolet light irradiation
Film.Film layer surface drying time is lower than 3 seconds.
Product bright luster 120, adhesion 1 grade, tensile strength 26.72MPa, flexibility 1.0mm, Tg are 29.7 DEG C,
Pencil hardness 2H, water absorption rate 35%, solvent resistance qualification (10%NaOH, non-whitening), modified aqueous polyurethane emulsion
(product before illumination) has good stability (be stored at room temperature 6 months not stratified).
Embodiment 4
Aqueous polyurethane 30.0g is slowly added to 5,6,7,8- tetrahydro -4- of curing agent under the conditions of stirring (500r/min)
(4'- aminomethyl phenyl) -7,7- dimethyl -6,8- methylene bridge -2- quinazoline amine 0.15g, the alkenyl modification acrylate 1g that comes into leaves,
The mixed liquor (dripping off for 30 minutes) of trimethylol-propane trimethacrylate 0.08g and methacrylic acid 5g, in 500r/min
Mixing speed under react 1h, then be added initiator 2- hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -1- third
Then product is layered in polyfluortetraethylene plate by 2 minutes obtained aqueous polyurethane films of ultraviolet light irradiation by ketone 0.02g.Film layer
Surface drying time is lower than 3 seconds.
Product bright luster 125, adhesion 1 grade, tensile strength 27.22MPa, flexibility 1.0mm, Tg are 34.3 DEG C,
Pencil hardness 2H, water absorption rate 31%, solvent resistance qualification (10%NaOH, non-whitening), modified aqueous polyurethane emulsion
(product before illumination) has good stability (be stored at room temperature 6 months not stratified).
Comparative example 1
Aqueous polyurethane 30.0g is added into the three-necked flask equipped with blender, the 250mL of constant pressure titration funnel, so
Revolving speed is transferred to 500r/min afterwards, 2h is sufficiently stirred, then aqueous polyurethane is taped against in polyfluortetraethylene plate and stands, be put into 50
DEG C baking oven film-forming for 24 hours.
The bright luster 100 of product, adhesion 1 grade, flexibility 1mm, tensile strength 4.35MPa, Tg are -30.76 DEG C,
Pencil hardness 2B, water absorption rate 178%, solvent resistance (10%NaOH bleaches) are unqualified.
Comparative example 2
Aqueous polyurethane 30.0g is slowly added to trimethylol propane trimethyl third under the conditions of stirring (500r/min)
Olefin(e) acid ester 0.08g, methacrylic acid 5g and curing agent 5,6,7,8- tetrahydro -4- (4'- aminomethyl phenyl) -7,7- dimethyl -6,8-
Initiator 2- hydroxy-2-methyl -1- is slowly added dropwise after mixing evenly (500r/min) in methylene bridge -2- quinazoline amine 0.15g
[4- (2- hydroxyl-oxethyl) phenyl] -1- acetone 0.02g, 2h reaction terminates, and then product is layered in polyfluortetraethylene plate and is passed through
Cross 3 minutes obtained aqueous polyurethane films of ultraviolet light irradiation.
The bright luster 106 of product, adhesion 1 grade, tensile strength 15.32MPa, flexibility 1.0mm, Tg are 24.4 DEG C,
Pencil hardness H, water absorption rate 110%, solvent resistance qualification (10%NaOH, non-whitening) have good stability and (stand 6 months not
Layering).
Comparative example 3
Aqueous polyurethane 30.0g is slowly dropped into acrylic acid 5.0g, pentaerythrite three under the conditions of stirring (700r/min)
The mixed liquor (half an hour drips off) of acrylate 0.08g and isobornyl methacrylate 1.5g, stirring (700r/min) are uniform
Afterwards, 1173 photoinitiator azodiisobutyronitrile 0.02g, 3h reactions are added dropwise with five-minute period terminates, and is then layered on product poly-
The modified photocuring aqueous polyurethane film layer of terpenyl is made in tetrafluoroethene plate after the ultraviolet light irradiation of 100w 3 minutes, produces
Product surface drying time is lower than 4 seconds.
Product bright luster 118, adhesion 1 grade, tensile strength 21.33MPa, flexibility 1.0mm, Tg are 16.5 DEG C,
Water absorption rate is 77%, solvent resistance qualification (non-whitening), pencil hardness H.
Embodiment 2, embodiment 3, embodiment 4, comparative example 1, comparative example 2 and 4 properties of product of comparative example are compared, it is long
The acrylate modified photocuring aqueous polyurethane of leaf alkenyl have faster film formation time, higher mechanical property, preferably
Hardness, thermal property and water resistance.
Claims (10)
1. a kind of preparation method for the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves, it is characterised in that: by aqueous polyurethane, length
After leaf alkenyl modification acrylate, methacrylic acid, curing agent and trimethylol-propane trimethacrylate are stirred to react, add
Enter initiator, modified aqueous polyurethane emulsion is made, modified aqueous polyurethane emulsion is passed through into ultraviolet light shape
At Green High Performance aqueous polyurethane.
2. the preparation method for the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves as described in claim 1, it is characterised in that: long
Leaf alkenyl acrylate the preparation method comprises the following steps: acrylic acid and longifolene are mixed, polymerization inhibitor and catalyst reaction, reaction knot is added
Shu Hou collects 113~120 DEG C of fraction at 0.6kPa, and as come into leaves alkenyl modification acrylate；Wherein, the matter of longifolene
1.8~2.5 times that dosage is acrylic acid quality are measured, the quality dosage of polymerization inhibitor is the 0.8~1.2% of acrylic acid quality, catalysis
The quality dosage of agent is the 2.8~3.6% of acrylic acid quality.
3. the preparation method for the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves as claimed in claim 2, it is characterised in that: long
Leaf alkenyl acrylate the preparation method comprises the following steps: acrylic acid and longifolene are mixed, polymerization inhibitor and catalyst is then added, in temperature
Under conditions of being 55~65 DEG C react 16~18h, filter out catalyst, add quality dosage be acrylic acid quality 0.8~
1.2% polymerization inhibitor steams unreacted longifolene and acrylic acid under decompression, and collects 113~120 DEG C at 0.6kPa and evaporate
Point, as come into leaves alkenyl modification acrylate.
4. the preparation method for the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves as claimed in claim 3, it is characterised in that: resistance
Poly- agent is phenthazine；Catalyst is phosphotungstic acid.
5. the preparation method of the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves as described in claim 1-4 any one,
Be characterized in that: will come into leaves alkenyl modification acrylate, methacrylic acid, curing agent and trimethylol-propane trimethacrylate
Mixed liquor instill aqueous polyurethane in, after being added dropwise, high-speed stirred 1-1.5 hour, initiator is then added, be made modification
Then aqueous polyurethane emulsion afterwards forms Green High Performance aqueous polyurethane by ultraviolet light.
6. the preparation method for the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves as claimed in claim 5, it is characterised in that: long
Leaf alkenyl modification acrylate, methacrylic acid, curing agent and trimethylol-propane trimethacrylate mixed liquor in 30-
It is dripped off in 40 minutes；High-speed stirred speed is 450-550r/min.
7. the preparation method of the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves as described in claim 1-4 any one,
Be characterized in that: the quality dosage of initiator be come into leaves alkenyl modification acrylate and methacrylic acid quality sum 0.2~
0.5%；The quality dosage of trimethylol-propane trimethacrylate is come into leaves alkenyl modification acrylate and methacrylic acid
The 1~2% of quality sum；The quality dosage of curing agent be come into leaves alkenyl modification acrylate and methacrylic acid quality sum 2~
3%；The mass ratio of alkenyl modification acrylate and methacrylic acid of coming into leaves is (1~3): 10；The quality of methacrylic acid is water
The 14-18% of property polyurethane quality.
8. the preparation method of the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves as described in claim 1-4 any one,
Be characterized in that: initiator is 2- hydroxy-2-methyl -1- [4- (2- hydroxyl-oxethyl) phenyl] -1- acetone；Curing agent is 1,2,3,
4,5,6,7,8- octahydro -2,2- dimethyl -1,3- endo-methylene group azophenlyene, 1,2,3,4,5,6,7,8,8 α, 10 α-decahydro -2,2- two
Methyl-1,3- endo-methylene group azophenlyene and 5,6,7,8- tetrahydro -4- (4'- aminomethyl phenyl) -7,7- dimethyl -6,8- methylene bridge -
At least one of 2- quinazoline amine.
9. the preparation method of the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves as described in claim 1-4 any one,
Be characterized in that: ultraviolet lamp irradiation power is 100-200w, and the ultraviolet lighting time is 30 seconds to 2 minutes.
10. the preparation method of the alkenyl acrylic ester modified water-soluble polyurethane that comes into leaves as described in claim 1-4 any one,
Be characterized in that: aqueous polyurethane solid content is 20-30%；The solid content of modified aqueous polyurethane emulsion is 30~40wt%；
Green High Performance aqueous polyurethane surface drying time is lower than 3 seconds.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111040169A (en) * | 2019-12-30 | 2020-04-21 | 南京林业大学 | Terpenoid or derivative thereof-based polysiloxane, preparation method thereof and modified two-component waterborne polyurethane |
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| CN106117451A (en) * | 2016-07-29 | 2016-11-16 | 同光（江苏）新材料科技有限公司 | A kind of preparation method of acrylic ester grafted modified aqueous polyurethane resin |
| CN108752535A (en) * | 2018-05-24 | 2018-11-06 | 南京林业大学 | A kind of preparation method of terpene modified photocuring aqueous polyurethane |
| JP2019026766A (en) * | 2017-08-01 | 2019-02-21 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion, and composite resin dispersion derived from the same |
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| CN105482046A (en) * | 2015-12-30 | 2016-04-13 | 江苏日出化工有限公司 | Method for preparing acrylic ester modified inorganic material-waterborne polyurethane emulsion |
| CN106117451A (en) * | 2016-07-29 | 2016-11-16 | 同光（江苏）新材料科技有限公司 | A kind of preparation method of acrylic ester grafted modified aqueous polyurethane resin |
| JP2019026766A (en) * | 2017-08-01 | 2019-02-21 | 宇部興産株式会社 | Aqueous polyurethane resin dispersion, and composite resin dispersion derived from the same |
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| CN111040169B (en) * | 2019-12-30 | 2021-09-24 | 南京林业大学 | Terpenoid polysiloxane, preparation method thereof and modified two-component waterborne polyurethane |
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