CN107418501A - The biodegradable UV curing adhesives of vegetable oil-based polyols type and preparation method - Google Patents
The biodegradable UV curing adhesives of vegetable oil-based polyols type and preparation method Download PDFInfo
- Publication number
- CN107418501A CN107418501A CN201710328653.6A CN201710328653A CN107418501A CN 107418501 A CN107418501 A CN 107418501A CN 201710328653 A CN201710328653 A CN 201710328653A CN 107418501 A CN107418501 A CN 107418501A
- Authority
- CN
- China
- Prior art keywords
- vegetable oil
- based polyols
- biodegradable
- acid
- prepolymers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- 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
-
- 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
- C08G18/36—Hydroxylated esters of higher fatty acids
-
- 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
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyurethanes Or Polyureas (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Biological Depolymerization Polymers (AREA)
Abstract
The invention belongs to UV to solidify technical field of polymer materials, discloses biodegradable UV curing adhesives of a kind of vegetable oil-based polyols type and preparation method thereof.The inventive method comprises the following steps：(1) mixture of diisocyanate and catalyst is added in vegetable oil-based polyols, heating response, obtains plant oil base PU prepolymers；(2) prepolymer of step (1) is cooled to 45~55 DEG C, adds (methyl) hydroxyalkyl acrylate, polymerization inhibitor reaction, obtain UV cured vegetable oil base PUA prepolymers；(3) UV cured vegetable oil base PUA prepolymers, free radical photo-initiation, reactive diluent, the auxiliary agent of step (2) are well mixed, obtain the biodegradable UV curing adhesives of vegetable oil-based polyols type.It had not only realized UV solidifications but also had had excellent biodegradable performance, so as to fundamentally solve adhesive family macromolecule material because being difficult to problem of environmental pollution caused by biodegradation.
Description
Technical field
The invention belongs to UV to solidify technical field of polymer materials, and more particularly to a kind of vegetable oil-based polyols type can biology
Degraded UV curing adhesives and preparation method thereof.
Background technology
UV curing materials have curing rate is fast, solidification energy consumption it is low it is low with temperature, VOC emission amount is small, the cured film degree of cross linking
The advantages that high and receive and be widely applied.But the raw material of traditional UV curing materials are mainly the propylene from fossil resources
Esters of gallic acid monomer and polyalcohol, prepared curing materials completely can not biodegradable or biodegradability it is very poor, it is long
Phase is remained in nature will cause greatly to endanger to environment.The biodegradation of polymer be under certain conditions, one
Fixed time interior energy resolves into the process of low molecule or small molecule by the effect of biology, microorganism and enzyme.Biodegradation refers to
Organic chemicals under the catalytic action of the various enzymes secreted by biology, by aoxidizing, reducing, hydrolyzing, dehydrogenation, a system such as dehalogenation
Row chemical reaction, makes the organic compound of the HMW of complexity switch to simple organic matter or inorganic matter (such as water, CO2) mistake
Journey.The research of biodegradable polyurethane resin is also more and more, and degradable polyurethane synthetic method can discuss in terms of two,
On the one hand be using natural degradable materials synthesis or be filled into polyurethane, be on the other hand to be dropped using artificial synthesized
Depolymerization compound carrys out synthesis of polyurethane.Mainly synthesized degradable is used using artificial synthesized degradable macromolecule synthesis of polyurethane
Polyalcohol or degradable diisocyanate with this partly or entirely to replace the polyurethane to synthesize when non-degradable used
Raw material, so as to synthesized degradable type polyurethane.Vegetable oil is a kind of renewable resource, and biodegradability is good, its molecule knot
Often contain more double bond and hydroxyl in structure, it is easy to be converted into polyhydroxy monomer, it is poly- to be such as applied to synthesis UV solidifications
Urethane acrylate, then it can increase substantially the biodegradability of UV curing materials.
The content of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide a vegetable oil base
The biodegradable UV curing adhesives of polyol type.
Another object of the present invention is to provide a kind of above-mentioned vegetable oil-based polyols type biodegradable UV solidifications gluing
The preparation method of agent.
The purpose of the present invention is realized by following proposal：
A kind of preparation method of the biodegradable UV curing adhesives of vegetable oil-based polyols type, comprises the following steps：
(1) plant oil base PU prepolymers：The mixture of diisocyanate and catalyst is added in vegetable oil-based polyols,
Heating response, obtain plant oil base PU prepolymers；
(2) UV cured vegetables oil base PUA prepolymers：The prepolymer of step (1) is cooled to 45~55 DEG C, added (methyl)
Hydroxyalkyl acrylate, polymerization inhibitor reaction, obtain UV cured vegetable oil base PUA prepolymers；
(3) the biodegradable UV curing adhesives of vegetable oil-based polyols type：By the UV cured vegetable oil bases of step (2)
PUA prepolymers, free radical photo-initiation, reactive diluent, auxiliary agent are well mixed, and obtain product.
Vegetable oil-based polyols described in step (1) are prepared by the method comprised the following steps：
1. according to the mol ratio 1 of Organic Alcohol and vegetable oil:4~1:8, the alkaline molten of Organic Alcohol is added after vegetable oil is heated
Liquid, the lower 40~80min of back flow reaction of 50~80 DEG C of stirrings obtain vegetable oil acid esters；
2. adding catalyst, oxidant into the vegetable oil acid esters of step 1., 40~70 DEG C of 5~8h of stirring reaction obtain ring
Oxygen vegetable oil acid esters；
3. nucleopilic reagent, solvent, catalyst, 50~2500W UV illumination are added into the epoxidized vegetable oil acid esters of step 2.
5~30min of reaction is penetrated, obtains vegetable oil-based polyols.
Step 1. described in vegetable oil be preferably tung oil, soybean oil, peanut oil, sesame oil, linseed oil and castor oil etc.
At least one of.
Described Organic Alcohol be preferably in methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol and the tert-butyl alcohol extremely
Few one kind.
The amount of alkali is preferably the 1~3% of plant oil quality in the alkaline solution.
Described alkali is preferably sodium hydroxide or potassium hydroxide.
Step 2. described in oxidant be preferably at least one of hydrogen peroxide and oxygen.
The mass ratio of oxidant used and epoxidized vegetable oil acid esters is preferably 1:1~3:1.
Described catalyst is preferably at least one of formic acid, acetic acid, propionic acid, phosphoric acid and sulfuric acid.
The amount of used catalyst is catalytic amount, is 0.1 preferably with the mass ratio of oxidant:1~1.0:1.
Step 3. described in nucleopilic reagent be preferably diethylamine, diethanol amine, 2 hydroxy ethylamine, 3- Propanolamines, three hydroxyls
Methylpropane, 2,2- dihydromethyl propionic acids, 2,2- dimethylolpropionic acids, hydroxyethyl methacrylate, hydroxy-ethyl acrylate, formyl
At least one of amine, acetamide and acrylamide etc..
The mol ratio of nucleopilic reagent used and epoxidized vegetable oil acid esters is preferably 1:1~4:1.
The amount of used catalyst is preferably the 1~9% of nucleopilic reagent and epoxidized vegetable oil acid esters gross mass.
Described catalyst is solid catalyst or liquid catalyst.
Described solid catalyst is preferably solid acid and/or cationic photoinitiator.
Described liquid catalyst is preferably acidic ion liquid and/or Bronsted acid.
Described solid acid is preferably phosphotungstic acid/silica-gel catalyst (HPW/SiO2)。
Described cationic photoinitiator is preferably diazol, diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfide
At least one of salt, iron arene salt, sulfonyloxy ketone and triaryl silica ether.
Described acidic ion liquid is preferably N- (4- sulfonic groups) butyl trimethylamines disulfate, N- (4- sulfonic groups) fourth
Base trimethylamine tosilate, N- (4- sulfonic groups) butyl triethylamines disulfate, N- (4- sulfonic groups) butyl triethylamine pair
Toluene fulfonate, N- (4- sulfonic groups) butyl imidazole disulfate, N- (4- sulfonic acid) butyl-pyridinium disulfate, N- (4- sulfonic acid
Base) butyl-pyridinium tosilate, N- (4- sulfonic groups) butyl-pyridinium metilsulfate, N- (4- sulfonic groups) butyl-pyridinium vinegar
At least one of hydrochlorate and N- methylimidazolium hydrogen sulphate salt.
Described Bronsted acid is preferably at least one of the concentrated sulfuric acid, acetic acid, phosphoric acid, p-methyl benzenesulfonic acid and pyrovinic acid.
Described solvent is preferably absolute ether, acetone, ethyl acetate, tetrahydrofuran, dichloromethane, chloroform, isopropanol
At least one of with isobutanol.The organic solvent is used to provide solution reaction environment, therefore its dosage can be entered as needed
Row adjustment.
The molecular structure such as following formula of the above-mentioned vegetable oil-based polyols being prepared：
In formula, R1For C1~C4 straight or branched alkyl, R2For nucleophilic group；N=0 or 1；1<m；0<m+s<4；6<l
+m+n+s+t<16。
In preparation method of the present invention, each component molfraction of step (1) and step (2) is：1 part of diisocyanate；Plant
1~1.2 part of thing based oil；1~1.2 part of (methyl) hydroxyalkyl acrylate；
Preferably, (methyl) hydroxyalkyl acrylate dosage is excessive, it is ensured that isocyanates reacts completely, does not remain, and mistake
(methyl) hydroxyalkyl acrylate of amount can also play a part of activated monomer, and participate in ultraviolet light solidification together.
The mass fraction of step (3) each component is：80~100 parts of UV cured vegetable oil base PUA prepolymers；Free radical light draws
Send out 1~5 part of agent；10~20 parts of reactive diluent.
Diisocyanate described in step (1) is aromatic series and/or aliphatic diisocyanate, preferably hexa-methylene
Diisocyanate, toluene di-isocyanate(TDI), PPDI, 4,4 '-methyl diphenylene diisocyanate and isophorone
At least one of diisocyanate.
Catalyst described in step (1) is preferably dibutyl tin laurate, and its dosage is catalytic amount, preferably with
The mass ratio of UV cured vegetable oil base PUA prepolymers is 0.1:100~0.15:100.
Heating response described in step (1) refers to 2~4h of reaction at 65~75 DEG C.
It is preferably to drip to add the mixture of diisocyanate and catalyst in vegetable oil-based polyols described in step (1)
Add, rate of addition is preferably 1~10g/min, or control adds in 0.5~1h.
It is preferably again by diisocyanate and the mixture of catalyst in step (1) after first vegetable oil-based polyols are heated
Add reaction.
Vegetable oil-based polyols are first dehydrated using preceding described in step (1), are depressurized preferably at 115~125 DEG C de-
2~3h of water.
The preferred reaction of heating response described in step (1) is untill-NCO group content reaches theoretical value.
(methyl) hydroxyalkyl acrylate described in step (2) can be hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid
At least one of hydroxy butyl ester, hydroxyethyl methacrylate, hydroxy propyl methacrylate and methacrylate.
Polymerization inhibitor described in step (2) is polymerization inhibitor commonly used in the art, preferably MEHQ
Or hydroquinones.Its dosage is conventional amount used, is 0.05 preferably with the weight ratio of (methyl) hydroxyalkyl acrylate:100~
1.5:100。
The time reacted described in step (2) is preferably 2~3h.The reaction is preferably reaction to free-NCO content
Less than 0.1%.Solvent can be removed by distillation after the reaction.
The addition of (methyl) hydroxyalkyl acrylate described in step (2), polymerization inhibitor is preferably to be added dropwise to add, and rate of addition is excellent
Elect 1~10g/min as, or control adds in 0.5~1h.
Free radical photo-initiation described in step (3) is 1- hydroxycyclohexyl phenyl ketones (Irgacure-184), 2- hydroxyls
Base -2- methyl isophthalic acids-phenylacetone (Irgacure-1173), 2- methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1-
Acetone (Irgacure-907), 2,4,6- trimethylbenzoy-diphenies phosphine oxide (TPO) and 2,4,6- trimethylbenzoyls
At least one of base phenyl-phosphonic acid ethyl ester (TPO-L).
Reactive diluent described in step (3) is (methyl) isobornyl acrylate, 1,6-HD double methacrylate,
At least one of tripropylene glycol double methacrylate, pentaerythritol triacrylate and trimethylolpropane trimethacrylate.
Auxiliary agent described in step (3) can be other conventional use of auxiliary agents of this area, mainly including plasticizer, coupling
Agent, defoamer, levelling agent etc., adjuvant used amount are conventional amount used, preferably with UV cured vegetable oil base PUA prepolymers
100 parts by weight meters, the plasticizer consumption are 0.1~0.5 parts by weight, and the coupling agent dosage is 0.1~0.5 parts by weight, institute
It is 0.1~0.5 parts by weight to state defoamer dosage, and the levelling agent dosage is 0.1~0.5 parts by weight.
The present invention provides the biodegradable UV curing adhesives of vegetable oil-based polyols type that the above method is prepared, its
Not only UV solidifications had been realized but also there is excellent biodegradable performance.
The present invention is had the following advantages and beneficial effect relative to prior art：
(1) vegetable oil-based polyols are substituted traditional petrochemical material polyalcohol by the present invention for polyurethane stock material, right
In widening natural oil lipid products application and improving its added value, the pressure of petrochemical industry is alleviated, by with positive reference
Value.
(2) the UV curing adhesives prepared by the present invention use biodegradable vegetable oil-based polyols as former material
Material, has excellent biodegradable performance, so as to fundamentally solve adhesive family macromolecule material because can not give birth to
Problem of environmental pollution caused by thing degraded.
Brief description of the drawings
Fig. 1 is the FT-IR spectrograms of the PUA oligomer synthesized by embodiment 1.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
The material being related in the following example can obtain from commercial channel.
Wherein, vegetable oil-based polyols are prepared by the following method to obtain：
(1) synthesis of methyl eleostearate and isolate and purify：43.6g tung oil (0.05mol, paulownia are added in 250mL three-necked flasks
Oil is calculated with eleostearic acid glyceride (872)), condensation reflux unit is installed, after thermostat water bath is heated to 80 DEG C, adds what is prepared
NaOH/ methanol solutions (0.436g/9.6g), wherein methanol：Tung oil=6:1 (mol/mol), methanol 0.3mol (9.6g)；NaOH
For 1% (0.436g) of tung oil quality；Magnetic agitation is opened, after reacting about 1h, stops reaction；Appropriate phosphoric acid is added to neutralize, while hot
Reaction solution is transferred to separatory funnel, stands, separates glycerin layer (lower floor)；The liquid on upper strata is washed 3~4 with hot distilled water
It is secondary, except the aqueous phase of sub-cloud, it is evaporated under reduced pressure and removes methanol and most of water etc., use anhydrous sodium sulfate drying；Obtain tung oil first
Esterification products.Tung oil methyl ester is isolated and purified using Silver nitrate silica gel column chromatograph method.
(2) synthesis of epoxy methyl eleostearate：30g methyl eleostearate is weighed in three-necked flask, is placed in 70 DEG C of water-bath
In and install agitating device, speed is arranged to 100r/min, and load onto condensation reflux unit.26.4g acetic acid is weighed, and
The 4 drop concentrated sulfuric acids are added, stirs, is then slowly dropped into methyl eleostearate, dripped off in 15min.Then 66g is weighed
30% hydrogenperoxide steam generator, be slowly dropped into three-necked flask, dripped off in 40min, and continue react 8h.Reaction terminates
Afterwards, its pH is adjusted to neutrality using 20% sodium carbonate liquor, is then transferred to separatory funnel stratification and divides sub-cloud.So
Wash afterwards with the deionized water of heat, now discovery water is on upper strata, and product is in lower floor.Ethyl acetate is added to be extracted into lower floor's product
Upper strata, the water of lower floor is separated, continue to use water repeated washing 3~5 times.Finally the ethyl acetate epoxy methyl eleostearate after washing is mixed
Close liquid to be transferred in beaker, add appropriate anhydrous sodium sulfate with abundant dry water removal, use Rotary Evaporators to remove acetic acid second
Ester, obtain epoxidation methyl eleostearate.
(3) synthesis of tung oil polylol：Weigh 10g epoxy methyl eleostearates, 10g diethanol amine, 10g isopropanol,
Stir；The triaryl sulfonium salts of 0.2g (epoxy methyl eleostearate and the 1% of diethanol amine gross mass) are weighed, with 10g acetone
It is fully dissolved.Above-mentioned solution is mixed and stirred for uniformly.It is then placed under 2500W UV light, with 50r/min stirring
Speed, irradiation reaction 5min.Then reacted product, extraction, filtering, distillation are dissolved using isopropanol.It is then transferred to point
In liquid funnel, washed 4~5 times using saturation sodium sulphate.Finally it is evaporated under reduced pressure, obtains tung oil polylol.
Embodiment 1
(1) synthesis of plant oil base PU prepolymers：The 1mol vegetable oil based polyatomics measured are sequentially added in a kettle
Alcohol, stir and be warming up to 115 DEG C, 65 DEG C are cooled to after decompression dehydration 2h, then add 1mol hexamethylene diisocyanates and
The mixture of 0.01mol catalyst dibutyltin dilaurylates, pay attention to controlling its rate of addition preferably to drip off in 2h, react 2h
Afterwards, during which sampling and measuring-NCO group content terminates until reaching theoretical value, first step reaction；
(2) synthesis of UV cured vegetables oil base PUA prepolymers：It is 55 DEG C by intermediate product cooling made from step (1), stirs
The mixture of lower addition 1mol hydroxy-ethyl acrylates and 0.02mol polymerization inhibitor MEHQs is mixed, reacts 3h, tracking-NCO bases
The content of group, when free-NCO content is less than 0.1%, stops reaction and steam solvent cooling discharge, obtain vegetable oil Quito
First alcohol type UV solidifies PUA prepolymers；
(3) preparation of the biodegradable UV curing adhesives of vegetable oil-based polyols type：By the 80g UV obtained by step (2)
Solidify PUA prepolymers, 1g free radical photo-initiation Irgacure-184,10g reactive diluents isobornyl acrylate, 0.1g to increase
Agent, 0.2g coupling agents, 0.1g defoamers, 0.5g levelling agents are moulded, mixes, stirs in proportion, that is, obtain vegetable oil based polyatomic
The biodegradable UV curing adhesives of alcohol type.
The examination of infrared spectrum of PUA oligomer：It is red using the type Fourier transforms of FT-IR 360 of Nicolet companies of the U.S.
External spectrum instrument, test scope are 400cm-1~4000cm-1, PUA prepolymers are applied on KBr pieces and tested, obtain sample
Infrared spectrogram, as shown in Figure 1.
Known by Fig. 1, in figure, 3370cm-1The absworption peak nearby occurred is N-H stretching vibration peaks, 1540cm-1Nearby go out
Existing absworption peak is N-H flexural vibrations peaks, 1720cm-1The absworption peak nearby occurred is C=O stretching vibration peak, indicates ammonia
The generation of carbamate (NHCOO) key；1637cm-1The absworption peak nearby occurred is C=C stretching vibration peaks, 1414cm-1Near
The absworption peak of appearance be double bond on C-H stretching vibration peak, 813cm-1The absworption peak nearby occurred is that the bending of C-H in double bond is shaken
Dynamic peak, indicates HEA and is connected on main chain；2270cm-1The characteristic absorption peak at place disappears, and-the NCO indicated in system is basic
Reaction is complete, and this shows to be successfully prepared vegetable oil-based polyols type UV solidification PUA prepolymers.
Embodiment 2
(1) synthesis of plant oil base PU prepolymers：The 1mol vegetable oil based polyatomics measured are sequentially added in a kettle
Alcohol, stir and be warming up to 125 DEG C, 75 DEG C are cooled to after decompression dehydration 3h, then add 1.2mol toluene di-isocyanate(TDI)s and
The mixture of 0.03mol catalyst dibutyltin dilaurylates, pay attention to controlling its rate of addition preferably to drip off in 3h, react 4h
Afterwards, during which sampling and measuring-NCO group content terminates until reaching theoretical value, first step reaction；
(2) synthesis of UV cured vegetables oil base PUA prepolymers：It is 45 DEG C by intermediate product cooling made from step (1), stirs
The mixture of lower addition 1.1mol hydroxypropyl acrylates and 0.01mol polymerization inhibitor MEHQs is mixed, reacts 3h, tracking-NCO
The content of group, when free-NCO content is less than 0.1%, stops reaction and steam solvent cooling discharge, obtain plant oil base
Polyol type UV solidifies PUA prepolymers；
(3) preparation of the biodegradable UV curing adhesives of vegetable oil-based polyols type：By the 100g obtained by step (2)
UV solidification PUA prepolymers, 5g free radical photo-initiation Irgacure-1173,20g reactive diluent methacrylic acid isoborneols
Ester, 0.1g plasticizer, 0.2g coupling agents, 0.1g defoamers, 0.5g levelling agents mix in proportion, stir, that is, obtain plant
The biodegradable UV curing adhesives of based oil type.
PUA oligomer is tested using the type Fourier transformation infrared spectrometers of FT-IR 360 of Nicolet companies of the U.S.
FTIR spectrograms, acquired results characteristic peak are same as Example 1.
Embodiment 3
(1) synthesis of plant oil base PU prepolymers：The 1mol vegetable oil based polyatomics measured are sequentially added in a kettle
Alcohol, stir and be warming up to 120 DEG C, 70 DEG C are cooled to after decompression dehydration 2.5h, then add 1.05mol PPDIs and
The mixture of 0.01mol catalyst dibutyltin dilaurylates, pay attention to controlling its rate of addition preferably to drip off in 2.5h, react 3h
Afterwards, during which sampling and measuring-NCO group content terminates until reaching theoretical value, first step reaction；
(2) synthesis of UV cured vegetables oil base PUA prepolymers：It is 45 DEG C by intermediate product cooling made from step (1), stirs
The mixture of lower addition 1mol hy-droxybutyls and 0.01mol polymerization inhibitor MEHQs is mixed, reacts 2h, tracking-NCO bases
The content of group, when free-NCO content is less than 0.1%, stops reaction and steam solvent cooling discharge, obtain vegetable oil Quito
First alcohol type UV solidifies PUA prepolymers；
(3) preparation of the biodegradable UV curing adhesives of vegetable oil-based polyols type：By the 100g obtained by step (2)
UV solidification PUA prepolymers, the double acrylic acid of 4g free radical photo-initiation Irgacure-907,15g reactive diluents 1,6-HD
Ester, 0.1g plasticizer, 0.1g coupling agents, 0.3g defoamers, 0.5g levelling agents mix in proportion, stir, that is, obtain plant
The biodegradable UV curing adhesives of based oil type.
PUA oligomer is tested using the type Fourier transformation infrared spectrometers of FT-IR 360 of Nicolet companies of the U.S.
FTIR spectrograms, acquired results characteristic peak are same as Example 1.
Embodiment 4
(1) synthesis of plant oil base PU prepolymers：The 1mol vegetable oil based polyatomics measured are sequentially added in a kettle
Alcohol, stir and be warming up to 125 DEG C, 75 DEG C are cooled to after decompression dehydration 3h, then adds 1.1mol4,4 '-diphenyl methane two is different
The mixture of cyanate and 0.03mol catalyst dibutyltin dilaurylates, pay attention to controlling its rate of addition preferably to drip off in 3h,
After reacting 4h, during which sampling and measuring-NCO group content terminates until reaching theoretical value, first step reaction；
(2) synthesis of UV cured vegetables oil base PUA prepolymers：It is 55 DEG C by intermediate product cooling made from step (1), stirs
The mixture of lower addition 1mol hydroxyethyl methacrylates and 0.01mol hydroquinone of polymerization retarder is mixed, reacts 3h, tracking-NCO bases
The content of group, when free-NCO content is less than 0.1%, stops reaction and steam solvent cooling discharge, obtain vegetable oil Quito
First alcohol type UV solidifies PUA prepolymers；
(3) preparation of the biodegradable UV curing adhesives of vegetable oil-based polyols type：By the 80g UV obtained by step (2)
Solidify PUA prepolymers, 1g free radical photo-initiation TPO, 10g reactive diluent tripropylene glycols double methacrylate, 0.2g plasticising
Agent, 0.3g coupling agents, 0.1g defoamers, 0.5g levelling agents mix in proportion, stir, that is, obtain vegetable oil-based polyols type
Biodegradable UV curing adhesives.
PUA oligomer is tested using the type Fourier transformation infrared spectrometers of FT-IR 360 of Nicolet companies of the U.S.
FTIR spectrograms, acquired results characteristic peak are same as Example 1.
Embodiment 5
(1) synthesis of plant oil base PU prepolymers：The 1mol vegetable oil based polyatomics measured are sequentially added in a kettle
Alcohol, stir and be warming up to 115 DEG C, 75 DEG C are cooled to after decompression dehydration 3h, then add 1mol IPDIs and
The mixture of 0.01mol catalyst dibutyltin dilaurylates, pay attention to controlling its rate of addition preferably to drip off in 3h, react 4h
Afterwards, during which sampling and measuring-NCO group content terminates until reaching theoretical value, first step reaction；
(2) synthesis of UV cured vegetables oil base PUA prepolymers：It is 55 DEG C by intermediate product cooling made from step (1), stirs
The mixture of lower addition 1.2mol hydroxy propyl methacrylates and 0.02mol hydroquinone of polymerization retarder is mixed, reacts 3h, tracking-NCO
The content of group, when free-NCO content is less than 0.1%, stops reaction and steam solvent cooling discharge, obtain plant oil base
Polyol type UV solidifies PUA prepolymers；
(3) preparation of the biodegradable UV curing adhesives of vegetable oil-based polyols type：By the 90g UV obtained by step (2)
Solidify PUA prepolymers, 2.5g free radical photo-initiation TPO-L, 15g reactive diluents pentaerythritol triacrylate, 0.3g to increase
Modeling agent, 0.2g coupling agents, 0.5g defoamers, 0.5g levelling agents mix in proportion, stir, that is, obtain vegetable oil-based polyols
The biodegradable UV curing adhesives of type.
PUA oligomer is tested using the type Fourier transformation infrared spectrometers of FT-IR 360 of Nicolet companies of the U.S.
FTIR spectrograms, acquired results characteristic peak are same as Example 1.
Embodiment 6
(1) synthesis of plant oil base PU prepolymers：The 1mol vegetable oil based polyatomics measured are sequentially added in a kettle
Alcohol, stir and be warming up to 120 DEG C, 70 DEG C are cooled to after decompression dehydration 2.5h, then add the isocyanic acid of 1.1mol hexa-methylenes two
The mixture of ester and 0.015mol catalyst dibutyltin dilaurylates, pay attention to controlling its rate of addition preferably to drip off in 2.5h,
After reacting 3h, during which sampling and measuring-NCO group content terminates until reaching theoretical value, first step reaction；
(2) synthesis of UV cured vegetables oil base PUA prepolymers：It is 50 DEG C by intermediate product cooling made from step (1), stirs
The mixture of lower addition 1mol methacrylates and 0.01mol hydroquinone of polymerization retarder is mixed, reacts 2.5h, tracking-NCO
The content of group, when free-NCO content is less than 0.1%, stops reaction and steam solvent cooling discharge, obtain plant oil base
Polyol type UV solidifies PUA prepolymers；
(3) preparation of the biodegradable UV curing adhesives of vegetable oil-based polyols type：By the 100g obtained by step (2)
UV solidification PUA prepolymers, 3g free radical photo-initiation TPO, 15g reactive diluents trimethylolpropane trimethacrylate, 0.2g
Plasticizer, 0.5g coupling agents, 0.1g defoamers, 0.1g levelling agents mix in proportion, stir, that is, obtain vegetable oil based polyatomic
The biodegradable UV curing adhesives of alcohol type.
PUA oligomer is tested using the type Fourier transformation infrared spectrometers of FT-IR 360 of Nicolet companies of the U.S.
FTIR spectrograms, acquired results characteristic peak are same as Example 1.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the biodegradable UV curing adhesives of vegetable oil-based polyols type, it is characterised in that including as follows
Step：
(1) plant oil base PU prepolymers：The mixture of diisocyanate and catalyst is added in vegetable oil-based polyols, heating
Reaction, obtains plant oil base PU prepolymers；
(2) UV cured vegetables oil base PUA prepolymers：The prepolymer of step (1) is cooled to 45~55 DEG C, adds (methyl) propylene
Sour hydroxyalkyl, polymerization inhibitor reaction, obtain UV cured vegetable oil base PUA prepolymers；
(3) the biodegradable UV curing adhesives of vegetable oil-based polyols type：The UV cured vegetable oil bases PUA of step (2) is pre-
Polymers, free radical photo-initiation, reactive diluent, auxiliary agent are well mixed, and obtain product.
2. the preparation method of the biodegradable UV curing adhesives of vegetable oil-based polyols type according to claim 1, its
It is characterised by：
Vegetable oil-based polyols described in step (1) are prepared by the method comprised the following steps：
1. according to the mol ratio 1 of Organic Alcohol and vegetable oil:4~1:8, the alkaline solution of Organic Alcohol is added after vegetable oil is heated,
Lower 40~the 80min of back flow reaction of 50~80 DEG C of stirrings obtains vegetable oil acid esters；
2. adding catalyst, oxidant into the vegetable oil acid esters of step 1., 40~70 DEG C of 5~8h of stirring reaction obtain epoxy plant
Thing oleate；
3. adding nucleopilic reagent, solvent, catalyst into the epoxidized vegetable oil acid esters of step 2., 50~2500WUV light irradiations are anti-
5~30min is answered, obtains vegetable oil-based polyols.
3. the preparation method of the biodegradable UV curing adhesives of vegetable oil-based polyols type according to claim 2, its
It is characterised by：
Step 1. described in vegetable oil be tung oil, soybean oil, peanut oil, sesame oil, linseed oil and castor oil at least one
Kind；
Described Organic Alcohol is at least one of methanol, ethanol, normal propyl alcohol, isopropanol, n-butanol, isobutanol and tert-butyl alcohol；
The amount of alkali is the 1~3% of plant oil quality in the alkaline solution；
Described alkali is sodium hydroxide or potassium hydroxide.
4. the preparation method of the biodegradable UV curing adhesives of vegetable oil-based polyols type according to claim 2, its
It is characterised by：
Step 2. described in oxidant be at least one of hydrogen peroxide and oxygen；
The mass ratio of oxidant used and epoxidized vegetable oil acid esters is 1:1~3:1.
5. the preparation method of the biodegradable UV curing adhesives of vegetable oil-based polyols type according to claim 2, its
It is characterised by：
Step 3. described in nucleopilic reagent for diethylamine, diethanol amine, 2 hydroxy ethylamine, 3- Propanolamines, trimethylolpropane,
2,2- dihydromethyl propionic acids, 2,2- dimethylolpropionic acids, hydroxyethyl methacrylate, hydroxy-ethyl acrylate, formamide, acetamide
At least one of with acrylamide；
The mol ratio of nucleopilic reagent used and epoxidized vegetable oil acid esters is 1:1~4:1；
The amount of used catalyst is the 1~9% of nucleopilic reagent and epoxidized vegetable oil acid esters gross mass；
Described catalyst is solid catalyst or liquid catalyst；
Described solid catalyst is solid acid and/or cationic photoinitiator；
Described liquid catalyst is acidic ion liquid and/or Bronsted acid；
Described solid acid is phosphotungstic acid/silica-gel catalyst；
Described cationic photoinitiator is diazol, diaryl group iodized salt, triaryl sulfonium salts, alkyl sulfosalt, iron virtue
At least one of hydrocarbon salt, sulfonyloxy ketone and triaryl silica ether；
Described acidic ion liquid is N- (4- sulfonic groups) butyl trimethylamines disulfate, N- (4- sulfonic groups) butyl trimethylamine
Tosilate, N- (4- sulfonic groups) butyl triethylamines disulfate, N- (4- sulfonic groups) butyl triethylamine p-methyl benzenesulfonic acid
Salt, N- (4- sulfonic groups) butyl imidazole disulfate, N- (4- sulfonic acid) butyl-pyridinium disulfate, N- (4- sulfonic groups) butyl pyrrole
Pyridine tosilate, N- (4- sulfonic groups) butyl-pyridinium metilsulfate, N- (4- sulfonic groups) butyl-pyridinium acetate and N-
At least one of methylimidazolium hydrogen sulphate salt；
Described Bronsted acid is at least one of the concentrated sulfuric acid, acetic acid, phosphoric acid, p-methyl benzenesulfonic acid and pyrovinic acid.
6. the preparation method of the biodegradable UV curing adhesives of vegetable oil-based polyols type according to claim 1, its
It is characterised by：
The each component molfraction of step (1) and step (2) is：1 part of diisocyanate；1~1.2 part of vegetable oil-based polyols；
1~1.2 part of (methyl) hydroxyalkyl acrylate；
The mass fraction of step (3) each component is：80~100 parts of UV cured vegetable oil base PUA prepolymers；Free radical photo-initiation
1~5 part；10~20 parts of reactive diluent.
7. the preparation method of the biodegradable UV curing adhesives of vegetable oil-based polyols type according to claim 1, its
It is characterised by：
Diisocyanate described in step (1) is hexamethylene diisocyanate, toluene di-isocyanate(TDI), to the isocyanic acid of benzene two
At least one of ester, 4,4 '-methyl diphenylene diisocyanate and IPDI；
Described catalyst is dibutyl tin laurate, and its dosage and the mass ratio of UV cured vegetable oil base PUA prepolymers are
0.1:100~0.15:100；
The heating response refers to 2~4h of reaction at 65~75 DEG C.
8. the preparation method of the biodegradable UV curing adhesives of vegetable oil-based polyols type according to claim 1, its
It is characterised by：
(methyl) hydroxyalkyl acrylate described in step (2) is hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid hydroxyl fourth
At least one of ester, hydroxyethyl methacrylate, hydroxy propyl methacrylate and methacrylate；
Described polymerization inhibitor is MEHQ or hydroquinones；Its dosage and the weight ratio of (methyl) hydroxyalkyl acrylate are
0.05:100~1.5:100；
The time of the reaction is 2~3h.
9. the preparation method of the biodegradable UV curing adhesives of vegetable oil-based polyols type according to claim 1, its
It is characterised by：
Free radical photo-initiation described in step (3) is 1- hydroxycyclohexyl phenyl ketones, 2- hydroxy-2-methyl -1- phenyl third
Ketone, 2- methyl -2- (4- morpholinyls) -1- [4- (methyl mercapto) phenyl] -1- acetone, 2,4,6- trimethylbenzoy-diphenies
At least one of phosphine oxide and 2,4,6- trimethylbenzoyl phenyl phosphinic acid ethyl esters；
Described reactive diluent is (methyl) isobornyl acrylate, 1,6-HD double methacrylate, tripropylene glycol pair
At least one of acrylate, pentaerythritol triacrylate and trimethylolpropane trimethacrylate；
Described auxiliary agent includes plasticizer, coupling agent, defoamer, levelling agent；
In terms of the parts by weight of UV cured vegetable oil base PUA prepolymers 100, the plasticizer consumption is 0.1~0.5 parts by weight, described
Coupling agent dosage is 0.1~0.5 parts by weight, and the defoamer dosage is 0.1~0.5 parts by weight, and the levelling agent dosage is 0.1
~0.5 parts by weight.
10. a kind of biodegradable UV curing adhesives of vegetable oil-based polyols type, it is characterised in that according to claim 1~9
Preparation method described in any one obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710328653.6A CN107418501B (en) | 2017-05-11 | 2017-05-11 | The biodegradable UV curing adhesive of vegetable oil-based polyols type and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710328653.6A CN107418501B (en) | 2017-05-11 | 2017-05-11 | The biodegradable UV curing adhesive of vegetable oil-based polyols type and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107418501A true CN107418501A (en) | 2017-12-01 |
| CN107418501B CN107418501B (en) | 2019-11-15 |
Family
ID=60425956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710328653.6A Active CN107418501B (en) | 2017-05-11 | 2017-05-11 | The biodegradable UV curing adhesive of vegetable oil-based polyols type and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107418501B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108516899A (en) * | 2018-06-25 | 2018-09-11 | 山东农业大学 | A kind of functional form slow-release or control-release fertilizer core and preparation method thereof based on biological based binder |
| CN108530989A (en) * | 2018-03-08 | 2018-09-14 | 广州美晶电脑图文科技有限公司 | A kind of tung oil base is modified UV solidification jetted inks and its preparation method and application |
| CN108530990A (en) * | 2018-03-08 | 2018-09-14 | 广州美晶电脑图文科技有限公司 | A kind of biology base is modified UV solidification jetted inks and its preparation method and application |
| CN108727515A (en) * | 2018-06-21 | 2018-11-02 | 中国热带农业科学院农产品加工研究所 | The chitosan-based polyalcohol of vegetable oil acid-is catalyzed the method for preparing the polyalcohol with free radical photo-initiation |
| CN108840990A (en) * | 2018-06-21 | 2018-11-20 | 华南农业大学 | Dual cross-linking type tung oil base UV cured polyurethane acrylate and its preparation method and application |
| CN108949092A (en) * | 2018-07-26 | 2018-12-07 | 龙游恒宇鞋业有限公司 | A kind of water-borne UV-curing adhesive and its preparation method and application |
| CN109180904A (en) * | 2018-08-31 | 2019-01-11 | 华南农业大学 | A kind of tung oil base Cationic Aqueous Polyurethane Emulsion and its preparation method and application |
| CN109306049A (en) * | 2018-09-28 | 2019-02-05 | 中国热带农业科学院农产品加工研究所 | Chitosan-based biodegradable PUA of vegetable oil-and its preparation method and application |
| CN109722093A (en) * | 2018-12-17 | 2019-05-07 | 赖贵尧 | A kind of laser transfer paper LED UV curing glue and preparation method thereof |
| CN111647360A (en) * | 2020-06-22 | 2020-09-11 | 上海朝荟新材料科技有限公司 | Formula and preparation method of degradable UV glue |
| CN111944119A (en) * | 2020-08-31 | 2020-11-17 | 上海奔佑新材料科技有限公司 | High-toughness material based on environment-friendly bio-based for 3D printing and preparation method thereof |
| CN112225901A (en) * | 2020-09-30 | 2021-01-15 | 华南理工大学 | Modified castor oil based UV (ultraviolet) curing polyurethane acrylate and preparation method thereof |
| CN112480347A (en) * | 2020-11-26 | 2021-03-12 | 上海应用技术大学 | Eucommia seed oil modified TPU and preparation method thereof |
| CN113307931A (en) * | 2021-05-31 | 2021-08-27 | 华南农业大学 | Plant oil-based flame-retardant polyurethane acrylate prepolymer and preparation method and application thereof |
| CN113416280A (en) * | 2021-05-28 | 2021-09-21 | 华南理工大学 | Ultraviolet-cured silicon-containing organic-inorganic hybrid resin and preparation method thereof |
| CN113683994A (en) * | 2021-10-12 | 2021-11-23 | 黑龙江省科学院石油化学研究院 | Modified cyanate ester-based adhesive and preparation method thereof |
| CN114213292A (en) * | 2021-11-17 | 2022-03-22 | 浩力森涂料（上海）有限公司 | Dual-curable vegetable oil modified isocyanate curing agent and preparation method thereof |
| CN115612443A (en) * | 2022-11-10 | 2023-01-17 | 福州大学 | Hyperbranched castor oil-based triple-response cured electronic protective adhesive and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110065821A1 (en) * | 2008-05-13 | 2011-03-17 | Cargill, Incorporated | Polyol made from partialy hydrogenated, fully epoxidized natural oils |
| CN105542702A (en) * | 2015-12-23 | 2016-05-04 | 华南理工大学 | Ultraviolet-cured polyurethane adhesive and preparation method thereof |
| CN105601880A (en) * | 2015-12-25 | 2016-05-25 | 何明辉 | Castor oil-based polyurethane acrylate and preparation method as well as application thereof |
-
2017
- 2017-05-11 CN CN201710328653.6A patent/CN107418501B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110065821A1 (en) * | 2008-05-13 | 2011-03-17 | Cargill, Incorporated | Polyol made from partialy hydrogenated, fully epoxidized natural oils |
| CN105542702A (en) * | 2015-12-23 | 2016-05-04 | 华南理工大学 | Ultraviolet-cured polyurethane adhesive and preparation method thereof |
| CN105601880A (en) * | 2015-12-25 | 2016-05-25 | 何明辉 | Castor oil-based polyurethane acrylate and preparation method as well as application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 姜诚 等: "植物油基多元醇的合成研究进展", 《化学与生物工程》 * |
| 贾连昆 等: "植物油多元醇的制备及其在聚氨酯胶粘剂中的应用", 《粘接》 * |
Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108530989A (en) * | 2018-03-08 | 2018-09-14 | 广州美晶电脑图文科技有限公司 | A kind of tung oil base is modified UV solidification jetted inks and its preparation method and application |
| CN108530990A (en) * | 2018-03-08 | 2018-09-14 | 广州美晶电脑图文科技有限公司 | A kind of biology base is modified UV solidification jetted inks and its preparation method and application |
| CN108840990B (en) * | 2018-06-21 | 2020-09-01 | 华南农业大学 | Dual-crosslinking tung oil-based UV-cured polyurethane acrylate and preparation method and application thereof |
| CN108727515A (en) * | 2018-06-21 | 2018-11-02 | 中国热带农业科学院农产品加工研究所 | The chitosan-based polyalcohol of vegetable oil acid-is catalyzed the method for preparing the polyalcohol with free radical photo-initiation |
| CN108840990A (en) * | 2018-06-21 | 2018-11-20 | 华南农业大学 | Dual cross-linking type tung oil base UV cured polyurethane acrylate and its preparation method and application |
| CN108727515B (en) * | 2018-06-21 | 2020-12-22 | 中国热带农业科学院农产品加工研究所 | Vegetable oleic acid-chitosan-based polyol and method for preparing same under catalysis of free radical photoinitiator |
| CN108516899A (en) * | 2018-06-25 | 2018-09-11 | 山东农业大学 | A kind of functional form slow-release or control-release fertilizer core and preparation method thereof based on biological based binder |
| CN108949092A (en) * | 2018-07-26 | 2018-12-07 | 龙游恒宇鞋业有限公司 | A kind of water-borne UV-curing adhesive and its preparation method and application |
| CN109180904A (en) * | 2018-08-31 | 2019-01-11 | 华南农业大学 | A kind of tung oil base Cationic Aqueous Polyurethane Emulsion and its preparation method and application |
| CN109306049B (en) * | 2018-09-28 | 2020-12-01 | 中国热带农业科学院农产品加工研究所 | Vegetable oil-chitosan-based biodegradable PUA as well as preparation method and application thereof |
| CN109306049A (en) * | 2018-09-28 | 2019-02-05 | 中国热带农业科学院农产品加工研究所 | Chitosan-based biodegradable PUA of vegetable oil-and its preparation method and application |
| CN109722093A (en) * | 2018-12-17 | 2019-05-07 | 赖贵尧 | A kind of laser transfer paper LED UV curing glue and preparation method thereof |
| CN111647360A (en) * | 2020-06-22 | 2020-09-11 | 上海朝荟新材料科技有限公司 | Formula and preparation method of degradable UV glue |
| CN111944119A (en) * | 2020-08-31 | 2020-11-17 | 上海奔佑新材料科技有限公司 | High-toughness material based on environment-friendly bio-based for 3D printing and preparation method thereof |
| CN112225901B (en) * | 2020-09-30 | 2022-03-29 | 华南理工大学 | Modified castor oil based UV (ultraviolet) curing polyurethane acrylate and preparation method thereof |
| CN112225901A (en) * | 2020-09-30 | 2021-01-15 | 华南理工大学 | Modified castor oil based UV (ultraviolet) curing polyurethane acrylate and preparation method thereof |
| CN112480347A (en) * | 2020-11-26 | 2021-03-12 | 上海应用技术大学 | Eucommia seed oil modified TPU and preparation method thereof |
| CN113416280A (en) * | 2021-05-28 | 2021-09-21 | 华南理工大学 | Ultraviolet-cured silicon-containing organic-inorganic hybrid resin and preparation method thereof |
| CN113307931A (en) * | 2021-05-31 | 2021-08-27 | 华南农业大学 | Plant oil-based flame-retardant polyurethane acrylate prepolymer and preparation method and application thereof |
| CN113307931B (en) * | 2021-05-31 | 2022-06-14 | 华南农业大学 | Plant oil-based flame-retardant polyurethane acrylate prepolymer and preparation method and application thereof |
| CN113683994A (en) * | 2021-10-12 | 2021-11-23 | 黑龙江省科学院石油化学研究院 | Modified cyanate ester-based adhesive and preparation method thereof |
| CN113683994B (en) * | 2021-10-12 | 2023-05-23 | 黑龙江省科学院石油化学研究院 | Modified cyanate-based adhesive and preparation method thereof |
| CN114213292A (en) * | 2021-11-17 | 2022-03-22 | 浩力森涂料（上海）有限公司 | Dual-curable vegetable oil modified isocyanate curing agent and preparation method thereof |
| CN115612443A (en) * | 2022-11-10 | 2023-01-17 | 福州大学 | Hyperbranched castor oil-based triple-response cured electronic protective adhesive and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107418501B (en) | 2019-11-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107418501B (en) | The biodegradable UV curing adhesive of vegetable oil-based polyols type and preparation method | |
| CN106866929A (en) | A kind of polyfunctionality castor oil-base light-cured resin and its preparation method and application | |
| CN106397719B (en) | Hyperbranched UV cured polyurethane acrylate of castor oil-base and its preparation method and application | |
| CN106750140B (en) | Amine modified urethane acrylate photocuring resin and preparation method thereof | |
| CN107189032B (en) | Multifunctional UV (ultraviolet) curing polyurethane vegetable oleate prepolymer and preparation method and application thereof | |
| CN107189750A (en) | A kind of biodegradable UV curing adhesives of tung oil base and its preparation method and application | |
| CN107987611B (en) | Hyperbranched resin-based UV (ultraviolet) curing inkjet ink and preparation method and application thereof | |
| CN101935385B (en) | Method for synthesizing low-hardness polyurethane acrylate | |
| CN106905504B (en) | Water-based ultraviolet-curing polyurethane resin and preparation method and application thereof | |
| CN104086742B (en) | A kind of preparation method of glass baseplate acid and alkali-resistance ultraviolet light solidified glue film resin | |
| CN106957406B (en) | A kind of calixarene type light-cured polyurethane resin and its coatings of preparation | |
| CN101274977B (en) | Curing agent 1,6- hexamethylene diisocyanate prepolymer and preparation thereof | |
| CN102911338B (en) | Multifunctional urethane acrylate oligomer as well as synthesis method and application thereof | |
| CN109266267A (en) | A kind of novel acrylic ester modified aqueous polyurethane binder | |
| CN103030777A (en) | Tung-oil-based polyurethane resin and preparation method thereof | |
| CN102617827B (en) | Curing agent modified 1,6-hexamethylene diisocyanate biuret (HDI biuret) and preparation method thereof | |
| CN103421462B (en) | High-initial-adhesion waterborne polyurethane adhesive and preparation method thereof | |
| CN110078893A (en) | Preparation method of ultraviolet-cured hyperbranched abienol polyurethane acrylate resin | |
| CN114181370A (en) | Modified urethane acrylate photocuring oligomer and preparation method thereof | |
| CN109438656A (en) | A kind of anacardol based polyurethanes acrylic resin and preparation method and application | |
| CN102432795B (en) | Sulfonated aqueous UV polyurethane modified epoxy acrylate emulsion and its preparation method | |
| CN108840990B (en) | Dual-crosslinking tung oil-based UV-cured polyurethane acrylate and preparation method and application thereof | |
| CN104559750A (en) | UV hand feeling coating based on elastic urethane acrylate and preparation method of UV hand feeling coating | |
| CN110016143B (en) | Multifunctional hybrid curing resin and preparation method thereof | |
| CN110746572A (en) | Dual-curing solvent-free polyurethane resin for automobile interior leather and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |