CN106519161A - Light-cured resin prepolymer, light-cured resin and preparation methods of light-cured resin prepolymer and light-cured resin - Google Patents
Light-cured resin prepolymer, light-cured resin and preparation methods of light-cured resin prepolymer and light-cured resin Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/428—Lactides
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- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
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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
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- C09D11/02—Printing inks
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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Abstract
The invention discloses a light-cured resin prepolymer, a light-cured resin and preparation methods of the light-cured resin prepolymer and the light-cured resin. The preparation method of the light-cured resin prepolymer comprises the following steps that 1, polyisocyanates with the mass being A is mixed with a diluent, a first catalyst is added, then polylactide polyhydric alcohols with the water content being lower than 500 ppm and the degree of functionality being larger than or equal to 2 are added dropwise, after all the alcohols are added dropwise, the temperature is increased to 70-80 DEG C, and a reaction is carried out for 1-2 hours; and 2, acrylate and/or methacrylate with the mass being B and containing one hydroxyl in the molecular structure is prepared, a second catalyst is added and mixed evenly, the mixture is dropwise added to the product obtained in the step 1, a reaction is carried out for 1-2 hours at the temperature of 70-80 DEG C, and thus the prepolymer is obtained, specifically, based on the value of A and the value of B, the ratio of the amount of substances of the contained hydroxyl to that of substances of isocyanate groups left after the reaction in the step 1 is 1-1.05. The light-cured resin prepared through the light-cured resin prepolymer has good mechanical strength after being cured, the cured product can be biodegraded under natural conditions, and pollution to the environment is little.
Description
【Technical field】
The present invention relates to light-cured resin, more particularly to a kind of light-cured resin performed polymer, light-cured resin and its system
Preparation Method.
【Background technology】
Light-cured resin is a kind of relatively low photoresist of relative molecular mass, with unsaturated double-bond or epoxy radicals etc.
Reactive group, light trigger can be activated under ultraviolet light or radiation of visible light carries out curing reaction.Light-cured resin is typically wrapped
Include performed polymer, monomer and light trigger.During illumination, light trigger produces active group under luminous energy effect, causes polymerization, crosslinking
Solidification is realized in reaction, liquid resin at short notice.
With the development of science and technology, photocuring technology is widely applied, especially in rapid shaping field.Light is solid
Change rapid shaping technique technological principle be：THREE DIMENSION GEOMETRIC MODELING is carried out to prototype using computer technology and STL etc. is processed into
The file of form, then model is carried out into cutting, horizontal cross-section lamellas parallel to each other a series of from bottom to top are formed, is calculated
Going out each section lamella generation includes optimal shortcut of both cross section profile path and internal scan paths, while in shaping system
To model orientation on system, supporting construction is designed；Command file of the routing information of slice information and generation as control forming machine,
And compile out the NC instruction feeding forming machine of every aspect.During Stereolithography, light-cured resin is contained in resin storage tank, resin
There are a lifting platform by computer controls, platform and resin surface or bottom interval certain thickness (0.025- above groove
0.1), make transverse and longitudinal scanning according to cross section profile by the light source of computer controls above resin storage tank, make a layer on lifting platform
Resin solidification.Subsequently lifting platform rises or falls certain altitude, makes cured resin layer surface cover one layer of new liquid tree
Fat, light source carry out transverse and longitudinal scanning again.The new curing resin layer that formed is securely bonded to one layer of following curing resin layer
Together, so repeat to finish until shaping.Compared with traditional Making mold, Introduction To Stereolithography speed is fast, production
Efficiency high, substantially reduces manufacturing time, saves manufacturing cost, and can be used for the mass production of high accuracy product, because
This is widely used in manufacturing industry.
However, current light-cured resin deposits the poor problem of mechanical strength after hardening, and it is difficult to degrade after solidifying, it is right
Environment has pollution.
【The content of the invention】
The technical problem to be solved is：Above-mentioned the deficiencies in the prior art are made up, a kind of light-cured resin is proposed
Performed polymer, light-cured resin and preparation method thereof, after obtained light-cured resin solidification, mechanical strength is preferable, and cured product can
Carry out biodegradable under field conditions (factors), environmental pollution is less.
The technical problem of the present invention is solved by following technical scheme：
A kind of preparation method of light-cured resin performed polymer, comprises the following steps：S1, by the polyisocyanates that quality is A
Mix with diluent, add the first catalyst, poly- third of degree of functionality of the water content less than 500ppm more than or equal to 2 is then added dropwise and hands over
Ester polyol, is warming up to 70～80 DEG C and reacts 1～2 hour after completion of dropping；Wherein, the amount of the material of isocyanate groups with it is poly-
In lactide polyalcohol, the ratio of the amount of the material of hydroxyl is more than 1；S2, prepares quality to contain a hydroxyl in the molecular structure of B
Acrylate and/or methacrylate, are added dropwise in adding the product that the second catalyst mixes obtained by backward step S1,70～
React 1～2 hour at 80 DEG C, performed polymer is obtained；Wherein, the value of A and B causes institute in acrylate and/or methacrylate
After reacting in the amount of the material of hydroxyl and step S1, the ratio of the amount of the material of remaining isocyanate groups is 1～1.05.
The light-cured resin performed polymer according to obtained in above-mentioned preparation method.
A kind of light-cured resin, including light-cured resin performed polymer as above, monomer, light trigger, auxiliary agent；By part
Number meter, the light-cured resin performed polymer are 50～80 parts, and the monomer is 0～50 part, and 0.5～5 part of light trigger, auxiliary agent are
0～1 part.
A kind of preparation method of light-cured resin, comprises the following steps：Outside dark or light trigger absworption peak wavelength
Under conditions of, heat at a temperature of 50～60 DEG C, 0～50 part of monomer, 0.5～5 part of light trigger, 0～1 part are helped
Agent mixes, and is well mixed which by stirring or ultrasonic wave；Then add 50～80 parts of light-cured resin as above
Performed polymer, after being well mixed by stirring or ultrasonic wave, is obtained light-cured resin.
The beneficial effect that the present invention is compared with the prior art is：
The light-cured resin performed polymer of the present invention, by isocyanates and polyalcohol pre-polymerization, isocyanate group is anti-with hydroxyl
Carbamate structures, and isocyanate group excess should be formed, it is then anti-with the isocyanate group of excess by monohydroxyl substances
End-blocking should be realized, while introducing the double bond needed for photocuring, light-cured resin performed polymer is obtained.Jing tests, the performed polymer and list
After body, light trigger, auxiliary agent constitute light-cured resin, the intensity after resin solidification is preferable.Simultaneously as realizing by biology
The polylactide polyol of base prepares light-cured resin, and the introducing of polylactide polyol is to the resistance to of light-cured resin cured product
Mill property and weatherability play humidification, while the biodegradable characteristic of material after solidification is given, so as to avoid environment dirty
Dye, reaches the purpose of environmental protection.The light-cured resin of the present invention can be widely applied to the neck such as coating, ink and photocuring 3D printing
Domain.
【Specific embodiment】
The present invention is described in further details with reference to specific embodiment.
This specific embodiment provides a kind of preparation method of light-cured resin performed polymer, comprises the following steps：
S1, polyisocyanates of the quality for A is mixed with diluent, the first catalyst is added, and water content is then added dropwise low
It is more than or equal to 2 polylactide polyol in the degree of functionality of 500ppm, 70～80 DEG C of reactions 1～2 is warming up to after completion of dropping little
When；Wherein, the amount of the material of isocyanate groups is more than 1 with the ratio of the amount of the material of hydroxyl in polylactide polyol.
In the step, polyisocyanates can be diisocyanate, and concretely diisocyanate is toluene diisocynate
Ester, methyl diphenylene diisocyanate, 1,5- naphthalene diisocyanates, hexamethylene diisocyanate, isophorone diisocyanate
In ester, XDI, cyclohexanedimethyleterephthalate diisocyanate, 4,4- dicyclohexyl methyl hydride diisocyanates
One or more of mixing.Certainly, in addition to for diisocyanate, polyisocyanates can also be many of three officials or higher functionality
Isocyanates.
Diluent can be 1,6 hexanediol diacrylate, ethoxylated neopentylglycol diacrylate, two contractings 3 third
The mixing of one or more in omega-diol diacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate.
Preferably, also it is mixed with water content to be more than less than 500ppm, degree of functionality in the polylactide polyol of above-mentioned addition
PPG equal to 2.PPG can be polyoxypropylene polyol, polytetrahydrofuran polyol, tetrahydrofuran-ring
The mixing of one or more in Ethylene Oxide copolyether.By adding PPG, obtained photo-cured products can be lifted
Pliability.During polylactide polyol is mixed with PPG, if polylactide polyol is added relatively
More, then after obtained light-cured resin solidification, mechanical strength is relatively preferable；If PPG adds relatively many,
After obtained light-cured resin solidification, pliability is relatively preferable.
In above-mentioned steps, polylactide polyol needs its water content less than 500ppm, so as to avoid hydrone and isocyanide
Acidic group produces side reaction and consumes isocyanates, causes the group ratio for designing out of control.As water content is excessive, ratio can be caused to lose
Control, understands gel when serious and causes to cancel.
Preferably, polylactide polyol or polylactide polyol and polyethers can be processed by way of vacuum stirring
The mixture of polyalcohol.Specifically, polylactide polyol or polylactide polyol are existed with the mixture of PPG
50～60 DEG C are cooled to after first stirring 1～2 hour under 100～120 DEG C, vacuum condition before dropwise addition, so, are on the one hand controlled
Polylactide polyol or polylactide polyol and the water content of the mixture of PPG, on the other hand can also slough
Volatile small molecule in polyalcohol or mixture and polylactide polyol and PPG are well mixed.
In the step, isocyanate group forms carbamate structures with hydroxyl reaction.The material of isocyanate groups
The amount of the material of the hydroxyl in mixture of the amount with polylactide polyol or middle polylactide polyol with PPG it
Than more than 1, to guarantee that isocyanate group excessively has residue, it is easy to subsequent step to be blocked with monohydroxyl substances reaction.It is preferred that
Ground, the ratio of the amount of both materials is 1.05～5.The amount of both materials is controlled below 5, so as to isocyanate groups
Amount is appropriate, is unlikely to remaining too many, then the mechanical property of subsequent cure product is preferable.
S2, prepares quality for the acrylate containing a hydroxyl and/or methacrylate in the molecular structure of B, addition
It is added dropwise in product obtained by backward step S1 of second catalyst mixing, reacts 1～2 hour at 70～80 DEG C, performed polymer is obtained；
Wherein, the value of A and B causes the amount of the material of institute's hydroxyl in acrylate and/or methacrylate and reaction in step S1
The ratio of the amount of the material of remaining isocyanate groups is 1～1.05 afterwards.
In the step, the acrylate containing a hydroxyl can be crylic acid hydroxy ester, the methacrylic acid containing a hydroxyl
Ester is methacrylic acid hydroxy ester.Crylic acid hydroxy ester can for acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate,
The mixing of one or more in hy-droxybutyl, trimethylolpropane diacrylate, pentaerythritol triacrylate.First
Base crylic acid hydroxy ester can be the one kind in hydroxy methyl methacrylate, hydroxyethyl methacrylate, methacrylate
Or various mixing.
In the step, the amount and step of the material of institute's hydroxyl in crylic acid hydroxy ester and/or methacrylic acid hydroxy ester
After reacting in S1 the amount of remaining isocyanate groups material quite, concretely 1～1.05.By the suitable single hydroxyl of introduction volume
Substratess matter, reacts remaining isocyanate groups (NCO) reaction end-blocking with previous step, reacts away remaining NCO group.
It should be noted that, step S1 step reaction the first catalyst used and the step reaction of step S2 the second catalyst used
Species can be with identical or different.Specifically, can be dibutyl tin laurate, stannous octoate, cobalt octoate, lead octoate, cycloalkanes
The mixing of any one or more in sour zinc.Preferably, the first catalyst or the second catalyst are di lauric dibutyl
Tin.Dibutyl tin laurate be organic tin catalyst, so as to its as this specific embodiment catalyst when, catalysis live
Property it is high, and and be unlikely to too fast and gel, be easy to control reaction.
Above by two-step reaction, performed polymer, specially base polyurethane prepolymer for use as is obtained.In preparation process, abandoning tradition
The organic solvent with volatility and toxicity such as acetone, toluene, from prepare photosensitive resin thinner composition as reaction
Solvent, has both reached dilution and has controlled the purpose of reaction rate, eliminated desolventizing link again, and Simplified flowsheet reduces VOC simultaneously
Discharge.In preparation process, realize and light-cured resin performed polymer is prepared by the polylactide polyol of bio-based, so as to obtained
There is biodegradable characteristic after light-cured resin solidification, biodegradable, the small molecule of degraded can be carried out under field conditions (factors)
Circulation is participated in product air inlet or soil, cured product can be avoided to remain after discarding and polluted in the environment, play guarantor
The effect in retaining ring border.
A kind of light-cured resin is also provided in this specific embodiment, including 50～80 parts of above-mentioned light-cured resin pre-polymerization
Body, 0～50 part of monomer, 0.5～5 part of light trigger, 0～1 part of auxiliary agent.
In above-mentioned formula, monomer can be acrylate, hydroxy-ethyl acrylate, hydroxypropyl acrylate, acrylic acid hydroxyl fourth
Ester, trimethylolpropane diacrylate, pentaerythritol triacrylate, hydroxy methyl methacrylate, hydroxyethyl methacrylate second
Ester, methacrylate, 1,6 hexanediol diacrylate, ethoxylated neopentylglycol diacrylate, two contractings 3 third
The mixing of one or more in omega-diol diacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate.
Light trigger be benzoin, α, alpha-alpha-dimethyl benzil ketals, 2- hydroxy-2-methyl -1- phenylacetones, 1- hydroxyls
Phenylcyclohexyl ketone, 2- benzyl -2- dimethylamino -1- (4- morpholinyl phenyls) -1- butanone, 2,4,6- trimethyl benzoyl diphenyls
The mixing of one or more in base phosphine oxide, double (2,4,6- trimethylbenzoyls) phenyl phosphine oxides.
Auxiliary agent includes one or more in polymerization inhibitor, levelling agent, defoamer, stabilizer, inhibitor.
A kind of preparation method of light-cured resin is also provided in this specific embodiment, is comprised the following steps：Dark or
Under conditions of outside light trigger absworption peak wavelength, heat at a temperature of 50～60 DEG C, by 0～50 part of monomer, 0.5～5
The light trigger of part, 0～1 part of auxiliary agent mixing, are well mixed which by stirring or ultrasonic wave；Then 50～80 parts are added
Light-cured resin performed polymer obtained as described above, by stirring or after ultrasonic wave is well mixed, light-cured resin is obtained.
The light-cured resin of this specific embodiment, is prepared from by above-mentioned performed polymer, so as to light-cured resin solidifies
There is biodegradable characteristic, and better mechanical property afterwards.By adjust in pre-polymerization production procedure polyester or polyester with
The species and ratio of polyethers and isocyanate index, are obtained the performed polymer of different soft and hard section content and physicochemical property, then lead to
The species and content of adjustment diluent, light trigger and auxiliary agent are crossed preparing light-cured resin, product after resin solidification is given
Different physico-chemical properties, especially mechanical property.Light-cured resin obtained in the performed polymer of this specific embodiment, mechanical property
It is good, it is nontoxic, it is environmentally friendly, can be used for ink, coating and photocuring 3D printing.
It is as follows, by specific experiment example verifying the mechanics of light-cured resin obtained in the performed polymer of this specific embodiment
Performance.
Experimental example 1：
In this experimental example, polylactide polyol used is polylactide dihydroxylic alcohols, and its structural formula is as follows：
Hydroxyl value is 220.53mg KOH g-1；Diisocyanate used be methyl diphenylene diisocyanate, isocyanates
Content is 30.0%.
Take the above-mentioned polylactide dihydroxylic alcohols of 50.9g to be placed in oil bath in 250ml there-necked flasks, 110 DEG C of heating are set, are opened
Stirring and vavuum pump are opened, heating is closed after 1 hour and is stirred；Take 56.0g methyl diphenylene diisocyanates and 60.0g1,6- oneself
Omega-diol diacrylate is mixed and added into 1 drop stannous octoate, is placed in 60 DEG C of oil baths, and above-mentioned polylactide binary is gradually added dropwise
Alcohol, is gradually heating to 70 DEG C and reacts 1 hour after being added dropwise to complete.Claim to obtain 1.0012g product, by titration isocyanate group mass contg
Standard HG/T 2409-92 titrated, it is 4.96% to obtain isocyanate content in product.From the titration results, can
Know that unreacted, remaining isocyanate groups amount are less, most of isocyanate groups react and reach expection.
22.8g hydroxy-ethyl acrylates are taken, is well mixed after 1 drop stannous octoate is added dropwise, is slowly dripped in above-mentioned product
Plus, 70 DEG C are kept after being added dropwise to complete and is reacted 1 hour, room temperature is cooled to after question response, water white liquid under room temperature is finally given
State performed polymer.Sampling 1.0032g product, titrate in product isocyanate content be 0, illustrate aforementioned remaining different
Cyanate group is blocked completely, no isocyanate group residual.
14.0g 1 is taken, 6- hexanediyl esters, 1.0g (2,4,6- trimethylbenzoyl) diphenyl phosphine oxide are mixed
Close, heat in 50 DEG C of water-baths, solid adds 100.0g performed polymers obtained above after all dissolving, mix 10 in ultrasonic wave
Minute, obtain light yellow clear liquid photocurable resin.
It is 2.11Pa s that viscosity of the above-mentioned light-cured resin at 25 DEG C is measured with rotation viscometer；Bottle method is measured
It is 1.20 to water proportion；GB detect tensile strength after resin solidification be 36.4MPa, elongation at break be 19.6%, it is curved
Qu Qiangdu is 16.3MPa, and impact strength is 20.7kJ/m2.Knowable to the test data, the mechanical property after resin solidification compared with
It is good.
Experimental example 2：
In this experimental example, polylactide polyol used is polylactide dihydroxylic alcohols, and its structural formula is as follows：
Hydroxyl value is 220.53mg KOH g-1；PPG used is PPG-400, and hydroxyl value is 280.35mg KOH g-1；Diisocyanate used is methyl diphenylene diisocyanate, and isocyanate content is 30.0%.
Take above-mentioned polylactide dihydroxylic alcohols 38.2g and PPG 30.0g and mix in 500ml there-necked flasks and be placed in
In oil bath, 110 DEG C of heating are set, stirring and vavuum pump is opened, after 1 hour, take out cooling；Take 126.0g diphenyl methanes two different
Cyanate and 130.0g1,6- hexanediyl ester are mixed and added into 3 drop dibutyl tin laurates, are placed in 60 DEG C of oil baths
In, the mixture of above-mentioned polylactide dihydroxylic alcohols and PPG is gradually added dropwise, 70 DEG C are gradually heating to after being added dropwise to complete instead
Answer 1 hour.Claim to obtain 1.0007g products, titrated by standard HG/T2409-92 of titration isocyanate group mass contg, produced
In thing, isocyanate content is 7.35%.The titration results show that isocyanate groups react and reach expection.
65.6g hydroxy-ethyl acrylates are taken, is well mixed after 1 drop stannous octoate is added dropwise, is slowly dripped in above-mentioned product
Plus, 70 DEG C are kept after being added dropwise to complete and is reacted 1 hour, room temperature is cooled to after question response, water white liquid under room temperature is finally given
State performed polymer.Sampling 1.0032g titrate product isocyanate content be 0.03%, illustrate aforementioned remaining isocyanates
Group is blocked completely, no isocyanate group residual.
14.0g1 is taken, 6- hexanediyl esters, 1.1g (2,4,6- trimethylbenzoyl) diphenyl phosphine oxide are mixed
Close, heat in 50 DEG C of water-baths, solid adds 120.0g performed polymers obtained above after all dissolving, mix 10 in ultrasonic wave
Minute, obtain light yellow clear liquid photocurable resin.
It is 1.76Pa s that viscosity of the above-mentioned light-cured resin at 25 DEG C is measured with rotation viscometer；Bottle method is measured
It is 1.17 to water proportion；GB detect tensile strength after resin solidification be 27.3MPa, elongation at break be 22.4%, it is curved
Qu Qiangdu is 10.9MPa, and impact strength is 12.2kJ/m2.Knowable to the test data, the mechanical property after resin solidification compared with
It is good.
Experimental example 3：
In this experimental example, polylactide polyol used is polylactide dihydroxylic alcohols, and its structural formula is as follows：
Hydroxyl value is 111.6mg KOH g-1；PPG used is PPG-1000, and hydroxyl value is 115.0mg KOH g-1；Diisocyanate used is methyl diphenylene diisocyanate, and isocyanate content is 30.0%.
Take above-mentioned polylactide dihydroxylic alcohols 50.3g and PPG 48.8g and mix in 500ml there-necked flasks and be placed in
In oil bath, 110 DEG C of heating are set, stirring and vavuum pump is opened, after 1 hour, take out cooling；Take two isocyanide of 70.0g diphenyl methanes
Acid esters and 60.0g tri (propylene glycol) diacrylates are mixed and added into 1 drop stannous octoate, are placed in 60 DEG C of oil baths, gradually drip
Plus the mixture for stating polylactide dihydroxylic alcohols and PPG, 70 DEG C are gradually heating to after being added dropwise to complete and are reacted 1 hour.Claim
1.0008g products are obtained, is titrated by the standard HG/T 2409-92 of titration isocyanate group mass contg, is obtained isocyanic acid in product
Ester group mass contg is 5.32%.The titration results show that isocyanate groups react and reach expection.
37.8g hydroxyethyl methacrylates are taken, is well mixed after 3 drop zinc naphthenates are added dropwise, is delayed in above-mentioned product
It is slow to be added dropwise, 70 DEG C are kept after being added dropwise to complete and is reacted 1 hour, room temperature is cooled to after question response, water white transparency under room temperature is finally given
Liquid prepolymer.Sampling 1.0002g titrate product isocyanate content be 0, illustrate aforementioned remaining isocyanates
Group is blocked completely, no isocyanate group residual.
Take 53.0g tri (propylene glycol) diacrylates, 2.0g (2,4,6- trimethylbenzoyls) diphenyl phosphine oxide
Mixing, heats in 50 DEG C of water-baths, and solid adds 100g performed polymers obtained above after all dissolving, mix 10 in ultrasonic wave
Minute, obtain light yellow clear liquid photocurable resin.
It is 1.90Pa s that viscosity of the above-mentioned light-cured resin at 25 DEG C is measured with rotation viscometer；Bottle method is measured
It is 1.16 to water proportion；GB detect tensile strength after resin solidification be 29.1MPa, elongation at break be 21.2%, it is curved
Qu Qiangdu is 14.3MPa, and impact strength is 18.6kJ/m2.Knowable to the test data, the mechanical property after resin solidification compared with
It is good.
Experimental example 4：
In this experimental example, polylactide polyol used is polylactide dihydroxylic alcohols A and polylactide polyol B.Poly- third
The structural formula of lactide polyalcohol A is as follows：
The structural formula of polylactide polyol B is as follows：
Wherein, the hydroxyl value of polylactide dihydroxylic alcohols A is 220.53mg KOH g-1, the hydroxyl value of polylactide polyol B is
558.39mg KOH·g-1；PPG is PPG-400, and hydroxyl value is 280.35mg KOH g-1；Diisocyanate is hexichol
Dicyclohexylmethane diisocyanate, isocyanate content are 30.0%.
Take 101.7g polylactides dihydroxylic alcohols A and 30.2g polylactide polyol B and 40.0g PPGs in
1000ml there-necked flasks are placed in oil bath, are arranged 110 DEG C of heating, are opened stirring and vavuum pump, close heating and stir after 1 hour
Mix；Take 252.0g methyl diphenylene diisocyanates and 270.0g1,6- hexanediyl ester is mixed and added into 3 drops octanoic acid
Stannous, are placed in 60 DEG C of oil baths, and above-mentioned polylactide dihydroxylic alcohols is gradually added dropwise, and 70 DEG C of reactions 1 are gradually heating to after being added dropwise to complete
Hour.Claim to obtain 1.0003g products, titrated by standard HG/T2409-92 of titration isocyanate group mass contg, obtained in product
Isocyanate content is 5.36%.The titration results show that isocyanate groups react and reach expection.
115.1g hydroxyethyl methacrylates are taken, is well mixed after 2 drop stannous octoates are added dropwise, is delayed in above-mentioned product
It is slow to be added dropwise, 70 DEG C are kept after being added dropwise to complete and is reacted 1 hour, room temperature is cooled to after question response, water white transparency under room temperature is finally given
Liquid prepolymer.Sampling 1.0032g titrate product isocyanate content be 0, illustrate aforementioned remaining isocyanates
Group is blocked completely, no isocyanate group residual.
Take 24.0g tri (propylene glycol) diacrylates, 4.8g trimethylolpropane trimethacrylates, 1.2g (2,4,6-
Trimethylbenzoyl) diphenyl phosphine oxide, the red slurry mixing of 1 drop, heat in 50 DEG C of water-baths, solid is added after all dissolving
The above-mentioned performed polymers of 90.0g, mix 10 minutes in ultrasonic wave, obtain red, transparent liquid photocurable resin.
It is 1.84Pa s that viscosity of the above-mentioned light-cured resin at 25 DEG C is measured with rotation viscometer；Bottle method is measured
It is 1.17 to water proportion；GB detect tensile strength after resin solidification be 39.6MPa, elongation at break be 26%, bending
Intensity is 18.5MPa, and impact strength is 15.3kJ/m2.Knowable to the test data, the mechanical property after resin solidification is preferable.
Experimental example 5：
In this experimental example, polylactide polyol used is polylactide dihydroxylic alcohols, and its structural formula is as follows：
Hydroxyl value is 220.53mg KOH g-1；PPG used is PPG-400, and hydroxyl value is 280.35mg KOH g-1；Diisocyanate used is hexamethylene diisocyanate, and isocyanate content is 49.5%.
Take above-mentioned polylactide dihydroxylic alcohols 38.2g and PPG 30.0g and mix in 250ml there-necked flasks and be placed in
In oil bath, 110 DEG C of heating are set, stirring and vavuum pump is opened, after 1 hour, take out cooling；Take two isocyanic acid of 50.9g hexa-methylenes
Ester and 50.0g1,6- hexanediyl ester are mixed and added into 1 drop stannous octoate, are placed in 65 DEG C of oil baths, are gradually added dropwise
Polylactide dihydroxylic alcohols and polyether polyol mixtures are stated, 70 DEG C is gradually heating to after being added dropwise to complete and is reacted 1 hour.Claim
1.0010g products, are titrated by the standard HG/T 2409-92 of titration isocyanate group mass contg, are obtained isocyanates in product
Group content is 7.06%.The titration results show that isocyanate groups react and reach expection.
32.8g hydroxy-ethyl acrylates are taken, is well mixed after 1 drop dibutyl tin laurate is added dropwise, to above-mentioned product
In be slowly added dropwise, be warming up to after being added dropwise to complete 75 DEG C react 1 hour, room temperature is cooled to after question response, nothing under room temperature is finally given
The transparent liquid prepolymer of color.Sampling 1.0032g titrate product isocyanate content be 0.05%, illustrate aforementioned residue
Isocyanate groups block completely, no isocyanate group residual.
Take 17.5g1, double (2,4,6- trimethylbenzoyl) phenyl phosphine oxides of 6- hexanediyl esters, 2.4g, 5
Drop defoamer, 5 drop levelling agents, the blue slurry mixing of 3 drops, heat in 50 DEG C of water-baths, and solid is added on 100.0g after all dissolving
Performed polymer is stated, is mixed 10 minutes in ultrasonic wave, is obtained blue-tinted transparent liquid photocurable resin.
It is 1.26Pa s that viscosity of the above-mentioned light-cured resin at 25 DEG C is measured with rotation viscometer；Bottle method is measured
It is 1.18 to water proportion；GB detect tensile strength after resin solidification be 23.3MPa, elongation at break be 27.1%, it is curved
Qu Qiangdu is 12.0MPa, and impact strength is 16.7kJ/m2.Knowable to the test data, the mechanical property after resin solidification compared with
It is good.
Experimental example 6：
In this experimental example, polylactide polyol used is polylactide dihydroxylic alcohols A and polylactide dihydroxylic alcohols B.Poly- third
The structural formula of lactide dihydroxylic alcohols A is as follows：
The structural formula of polylactide trihydroxylic alcohol B is as follows：
Wherein, polylactide dihydroxylic alcohols A hydroxyl values are 220.53mg KOH g-1, polylactide trihydroxylic alcohol B hydroxyl values are
558.33mg KOH·g-1；PPG C used is PPG-400, and hydroxyl value is 280.35mg KOH g-1；Polyethers used is more
First alcohol D is PTMG-500, and hydroxyl value is 229.86mg KOH g-1。
Take above-mentioned polylactide dihydroxylic alcohols A 101.8g, polylactide trihydroxylic alcohol B 60.3g and PPG C
80.0g, D 97.6g mixes in 2L there-necked flasks and is placed in oil bath, arranges 110 DEG C of heating, opens stirring and vavuum pump, and 1
Cooling is taken out after hour；Take 305.5g hexamethylene diisocyanates and 280.0g trimethylolpropane trimethacrylates mix simultaneously
Add 5 to drip stannous octoate, be placed in 65 DEG C of oil baths, the mixing of above-mentioned polylactide polyol and PPG is gradually added dropwise
Thing, is gradually heating to 70 DEG C and reacts 1 hour after being added dropwise to complete.Claim to obtain 1.0001g products, by the mark of titration isocyanate group mass contg
Quasi- HG/T 2409-92 are titrated, and in obtaining product, isocyanate content is 7.92%.The titration results show isocyanide
Acid esters group reacts and reaches expection.
101.2g hydroxy-ethyl acrylates, 113.4g hydroxyethyl methacrylates are taken, mixing is equal after 3 drop stannous octoates are added dropwise
It is even, it is slowly added dropwise in above-mentioned product, 75 DEG C is gradually heating to after being added dropwise to complete and is reacted 1 hour, be cooled to after question response
Room temperature, finally gives water white liquid prepolymer under room temperature.Sampling 1.0011g titrates to obtain product isocyanate content
For 0, illustrate that aforementioned remaining isocyanate groups are blocked completely, no isocyanate group residual.
Take 50.0 hydroxy methyl methacrylates, 150.0g tri (propylene glycol) diacrylates, 50.0g trimethylolpropanes
Triacrylate, 5.0g2,4,6- trimethyl benzoyl diphenyl base phosphine oxides, 3.0g are double (2,4,6- trimethylbenzoyls)
Phenyl phosphine oxide, 5 drop stock white mixing, heat in 50 DEG C of water-baths, and solid adds the above-mentioned performed polymers of 500.0g after all dissolving,
Mix 20 minutes in ultrasonic wave, obtain light yellow clear liquid photocurable resin.
It is 0.51Pa s that viscosity of the above-mentioned light-cured resin at 25 DEG C is measured with rotation viscometer；Bottle method is measured
It is 1.20 to water proportion；GB detect tensile strength after resin solidification be 37.1MPa, elongation at break be 29.4%, it is curved
Qu Qiangdu is 16.7MPa, and impact strength is 20.3kJ/m2。
Above content is with reference to specific preferred embodiment further description made for the present invention, it is impossible to assert
The present invention be embodied as be confined to these explanations.For general technical staff of the technical field of the invention,
Some replacements or obvious modification are made on the premise of without departing from present inventive concept, and performance or purposes are identical, should all be considered as
Belong to protection scope of the present invention.
Claims (10)
1. a kind of preparation method of light-cured resin performed polymer, it is characterised in that：Comprise the following steps：S1, is many of A by quality
Isocyanates is mixed with diluent, adds the first catalyst, and the degree of functionality that water content is then added dropwise less than 500ppm is more than or equal to 2
Polylactide polyol, be warming up to after completion of dropping 70～80 DEG C react 1～2 hour；Wherein, the material of isocyanate groups
The ratio of amount and the amount of the material of hydroxyl in polylactide polyol be more than 1；S2, prepares quality to contain one in the molecular structure of B
The acrylate and/or methacrylate of individual hydroxyl, drips in adding the product obtained by backward step S1 of the second catalyst mixing
Plus, react 1～2 hour at 70～80 DEG C, performed polymer is obtained；Wherein, the value of A and B causes acrylate and/or metering system
After reacting in the amount of the material of institute's hydroxyl and step S1 in acid esters the ratio of the amount of the material of remaining isocyanate groups be 1～
1.05。
2. the preparation method of light-cured resin performed polymer according to claim 1, it is characterised in that：In step S1, it is added dropwise
Polylactide polyol in be also mixed with water content less than 500ppm, degree of functionality more than or equal to 2 PPG.
3. the preparation method of light-cured resin performed polymer according to claim 2, it is characterised in that：The PPG
For the mixed of one or more in polyoxypropylene polyol, polytetrahydrofuran polyol, THF-PO copolymer
Close.
4. the preparation method of light-cured resin performed polymer according to claim 1, it is characterised in that：In step S1, isocyanide
The amount of the material of acid esters group is 1.05～5 with the ratio of the amount of the material of hydroxyl in polylactide polyol.
5. the preparation method of light-cured resin performed polymer according to claim 1, it is characterised in that：In step S1, poly- third
Lactide polyalcohol before dropwise addition, also including following processing procedure：After stirring 1～2 hour under 100～120 DEG C, vacuum condition
It is cooled to 50～60 DEG C.
6. the preparation method of light-cured resin performed polymer according to claim 1, it is characterised in that：In step S2, containing one
The acrylate of individual hydroxyl is crylic acid hydroxy ester；Or, the methacrylate containing a hydroxyl is methacrylic acid hydroxyl
Ester.
7. the preparation method of light-cured resin performed polymer according to claim 1, it is characterised in that：First catalyst
Or second catalyst be dibutyl tin laurate.
8. light-cured resin performed polymer obtained in preparation method according to claims 1 to 7.
9. a kind of light-cured resin, it is characterised in that：Including light-cured resin performed polymer as claimed in claim 8, monomer, light
Initiator, auxiliary agent；Based on number, the light-cured resin performed polymer is 50～80 parts, and the monomer is 0～50 part, light-initiated
0.5～5 part of agent, auxiliary agent are 0～1 part.
10. a kind of preparation method of light-cured resin, it is characterised in that：Comprise the following steps：Absorb in dark or light trigger
Under conditions of outside spike length, heat at a temperature of 50～60 DEG C, by 0～50 part of monomer, 0.5～5 part of light trigger,
0～1 part of auxiliary agent mixing, is well mixed which by stirring or ultrasonic wave；Then add 50～80 parts such as claim 8
Described light-cured resin performed polymer, after being well mixed by stirring or ultrasonic wave, is obtained light-cured resin.
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