CN102010494A - Light-cured resin with low water absorption and preparation method thereof - Google Patents
Light-cured resin with low water absorption and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a light-cured resin with low water absorption and a preparation method thereof. The light-cured resin is silicane modified hydroxyl-terminated polybutadiene type urethane acrylate. The preparation method comprises the following steps of: 1) reacting an epoxy silicane coupling agent with a primary amine silicane coupling agent to generate a modified silicane chain extender; 2) reacting hydroxyl-terminated polybutadiene with diisocyanate to generate polyurethane prepolymer 1; 3) reacting the modified silicane chain extender with the polyurethane prepolymer 1 to generate polyurethane prepolymer 2; and 4) reacting the polyurethane prepolymer 2 with hydroxyl acrylate to generate the silicane modified hydroxyl-terminated polybutadiene type urethane acrylate.
Description
Technical field
The present invention relates to a kind of light-cured resin with low water absorption and preparation method thereof, the occasion that it is applicable to high water-fast demand belongs to the photo-curing material field.
Background technology
Numerous outstanding advantages such as photo-curing material is fast owing to its curing speed, environmental friendliness, energy-output ratio are few, solvent-free volatilization obtain broad research, and promote rapidly in all trades and professions.But the photo-curing material of conventional polyurethanes esters of acrylic acid has the limitation of itself, and in the occasion of high water-fast demand was arranged, the conventional polyurethanes acrylate was difficult to meet the demands; The water-intake rate of conventional polyether polyurethane-acrylate is greater than 1%, the water-intake rate of normal polyester type polyurethane acrylate is greater than 2%, and the occasion that has needs water-intake rate less than 0.5%, and this just requires us to synthesize the urethane acrylate with low water absorption.
Organosilicon material is owing to its unique molecular structure has the performance of many excellences, and as high-temp resisting high-humidity resisting, weathering resistance, ageing resistance, electrical insulating property, low surface energy, its hydrophobic molecular structure makes it have extremely low water-intake rate; Polymer diatomic alcohol HTPB (hydroxy-terminated polybutadienes), the polyhutadiene main chain makes polymkeric substance have polymer properties such as similar natural rubber and isoprene-isobutylene rubber, have stronger hydrophobicity, cured article has excellent mechanical property, and the transparency is good, have excellent hydrolytic resistance, electrical insulating property, resistance to acids and bases especially, excellent low temperature kindliness, ageing-resistant, better to nonpolar and low polar adhesion, resistance to air loss is good, and moisture transmission is very low.
Organosilicon polyurethane acrylate (SPUA) is a kind of novel block macromolecular material that urethane, acrylate and silane coupling agent make by NCO group and reactive with active hydrogen.The synthetic method of existing organosilicon polyurethane acrylate mainly contains three kinds: the one, make with two hydroxy silicon oils, vulcabond and hydroxy acrylate reaction; The 2nd, make with two amido silicon oils, vulcabond and hydroxy acrylate reaction; The 3rd, silane coupling agent, polyurethane macromolecular and acrylate monomer ternary emulsion copolymerization reaction make; There are some problems in these several synthetic methods: at first the product consistency that obtains of reaction is bad, is difficult to the resin compatible with other systems; The 2nd, the bad control of reaction in the synthesis technique, the reaction of the primary amine groups of amido silicon oil and NCO group is very violent, is difficult to stable control; The 3rd, the synthetic molecular weight of product is less, and the molecular weight distribution broad.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of light-cured resin with low water absorption and preparation method thereof is provided, the product consistency is good to reach, the good control of reaction in the synthesis technique, the synthetic molecular weight of product is big and the narrower purpose of molecular weight distribution.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of light-cured resin with low water absorption, described light-cured resin are silane-modified hydroxy-terminated polybutadienes HTPB type polyurethane acrylate, and its structural formula is represented by following general formula (I):
Wherein: R
1, R
2, R
3Represent CH
3-, C
2H
5O-or CH
3O-, R represent tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate or hexamethylene diisocyanate etc.
The another technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of light with low water absorption
The preparation method of light-cured resin, wherein R
1, R
2, R
3, R definition such as in formula I definition, may further comprise the steps:
1) generate the modified silane chainextender by epoxy silane coupling and the reaction of primary amino silane coupling agent, its structural formula is represented by following general formula (II):
2) generate base polyurethane prepolymer for use as one by hydroxy-terminated polybutadienes and di-isocyanate reaction, its structural formula is represented by following general formula (III):
3) (II) formula and the reaction of (III) formula are generated base polyurethane prepolymer for use as two, its structural formula is represented by following general formula (IV):
4) (IV) formula and hydroxy acrylate reaction are generated silane-modified hydroxy-terminated polybutadienes type polyurethane acrylate.
On the basis of technique scheme, the present invention can also do following improvement.
Further, the synthesizing of modified silane chainextender in the described step 1): epoxy silane coupling is joined in the primary amino silane coupling agent, being warming up to 50～90 ℃ after mixing reacted 1～3 hour down, obtain containing the modified silane chainextender of secondary amino group and hydroxy functional group, the mol ratio of described epoxy silane coupling and primary amino silane coupling agent is 1.0～1.3: 1.
Further, described step 2) synthesizing of base polyurethane prepolymer for use as one described in: with hydroxy-terminated polybutadienes, in 100～115 ℃, vacuum tightness≤-0.08MPa, vacuumized 1.5～3 hours, remove wherein adulterated moisture; Be cooled to 40～60 ℃ then, add vulcabond, treat to be warmed up to 70～90 ℃ of reactions 1～3 hour after the homo(io)thermism, stop heating when NCO content reaches design load, promptly getting two ends is the base polyurethane prepolymer for use as one of NCO group; The mol ratio of described vulcabond and hydroxy-terminated polybutadienes is 1.5～2.3: 1.
Further, synthesizing of base polyurethane prepolymer for use as two described in the described step 3): behind above-mentioned base polyurethane prepolymer for use as that makes one and modified silane chainextender mixing, reacted 1～3 hour down at 70～90 ℃, promptly get the base polyurethane prepolymer for use as two that there is the NCO group at two ends, the mol ratio of described modified silane chainextender and base polyurethane prepolymer for use as one is 0.1～0.3: 1.
Further, the described silane-modified hydroxy-terminated polybutadienes type polyurethane acrylate of described step 4): behind base polyurethane prepolymer for use as two and hydroxy acrylate mixing, reacted 1～3 hour down at 60～80 ℃, obtain silane-modified type polyurethane acrylate, described base polyurethane prepolymer for use as two is 0.4～0.5: 1 with the mol ratio of hydroxy acrylate.
Further, the epoxy silane coupling described in the described step 1) is γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH-560) or γ-(2,3-epoxy third oxygen) propyl group methyl dimethoxysilane (WD-61).
Further, the primary amino silane coupling agent described in the described step 1) is γ-An Bingjisanyiyangjiguiwan (KH-550), γ-aminopropyl methyldiethoxysilane (WD-57) or γ-An Bingjisanjiayangjiguiwan (WD-56).
Further, the vulcabond described step 2) is a kind of or any several mixture in tolylene diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethanediisocyanate (MDI) or the hexamethylene diisocyanate (HDI).
Further, the hydroxy acrylate described in the described step 4) is a kind of or any several mixture in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or the Rocryl 410.
The invention has the beneficial effects as follows: adopting silane and HTPB with hydrophobic structure is raw material, has extremely low water-intake rate; The silane-modified HTPB type polyurethane of synthetic acrylate is a side chain type silicane-modified polyurethane acrylate, and the organosilicon segment is on the side chain of urethane acrylate, and this has higher body intensity and better water tolerance than backbone chain type urethane acrylate; Simple, the control easily of synthesis process does not need to use special equipment, and solvent-free, production cost is low; The silane-modified HTPB type polyurethane of synthetic acrylate structural is regular, molecular weight distribution is narrower.
Embodiment
Below principle of the present invention and feature are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
Embodiment 1
Take by weighing 10g γ-An Bingjisanyiyangjiguiwan (KH-550) and join 11g γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH-560) places there-necked flask, being warming up to 70 ℃ after mixing reacted 2 hours down, obtain containing the modified silane chainextender of secondary amino group and hydroxy functional group, its structural formula is:
Wherein, R
1, R
2, R
3Represent CH
3-, C
2H
5O-or CH
3O-;
100g HTPB is vacuumized under 110 ℃ (vacuum tightness≤-0.08MPa) 2 hours is to remove wherein adulterated moisture; Be cooled to 50 ℃ then, add 28.5g TDI, treat to be warmed up to 85 ℃ of reactions 2 hours after the homo(io)thermism, stop heating when NCO content reaches design load, promptly obtaining two ends is the base polyurethane prepolymer for use as one of NCO group, and its structural formula is:
,
Wherein, R represents tolylene diisocyanate;
Behind 100g base polyurethane prepolymer for use as one and 5.6g modified silane chainextender mixing, reacted 2 hours down at 80 ℃, promptly get the base polyurethane prepolymer for use as two that there is the NCO group at two ends, its structural formula is:
Wherein, R
1, R
2, R
3Represent CH
3-, C
2H
5O-or CH
3O-, R represents tolylene diisocyanate.
Behind 100g base polyurethane prepolymer for use as two and 6.9g Hydroxyethyl acrylate mixing, reacted 2 hours down at 70 ℃, obtain silane-modified HTPB (hydroxy-terminated polybutadienes) type polyurethane acrylate, its structural formula is:
Wherein, R
1, R
2, R
3Represent CH
3-, C
2H
5O-or CH
3O-, R represents tolylene diisocyanate.
Embodiment 2
Take by weighing 10g γ-An Bingjisanyiyangjiguiwan (KH-550) and join 11g γ-(2,3-epoxy third oxygen) propyl group methyl dimethoxysilane (WD-61) places there-necked flask, being warming up to 50 ℃ after mixing reacted 3 hours down, obtain containing the modified silane chainextender of secondary amino group and hydroxy functional group, same with embodiment 1;
100g HTPB is vacuumized under 100 ℃ (vacuum tightness≤-0.08MPa) 3 hours is to remove wherein adulterated moisture; Be cooled to 60 ℃ then, add 24g IPDI, treat to be warmed up to 80 ℃ of reactions 3 hours after the homo(io)thermism, when reaching design load, NCO content stops heating, promptly obtaining two ends is the base polyurethane prepolymer for use as one of NCO group, and its structural formula and embodiment 1 are same, and R represents isophorone diisocyanate.
Behind 100g base polyurethane prepolymer for use as one and 4.6g modified silane chainextender mixing, 70 ℃ of down reactions 3 hours, promptly get to the base polyurethane prepolymer for use as two that there is the NCO group at two ends, its structural formula and with embodiment 1, wherein, R
1, R
2, R
3Represent CH
3-, C
2H
5O-or CH
3O-, R represents isophorone diisocyanate.
With behind 100g base polyurethane prepolymer for use as two and the 6.3g hydroxyethyl methylacrylate mixing, 60 ℃ of reactions 3 hours down, obtain silane-modified HTPB (hydroxy-terminated polybutadienes) type polyurethane acrylate, its structural formula with embodiment 1, wherein, R
1, R
2, R
3Represent CH
3-, C
2H
5O-or CH
3O-, R represents isophorone diisocyanate.
Embodiment 3
Take by weighing 10g γ-aminopropyl methyldiethoxysilane (WD-57) and join 10g γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH-560) places there-necked flask, being warming up to 90 ℃ after mixing reacted 1 hour down, obtain containing the modified silane chainextender of secondary amino group and hydroxy functional group, itself and embodiment 1 are together;
100g HTPB is vacuumized under 115 ℃ (vacuum tightness≤-0.08MPa) 1.5 hours is to remove wherein adulterated moisture; Be cooled to 40 ℃ then, add 31g MDI, treat to be warmed up to 90 ℃ of reactions 1 hour after the homo(io)thermism, when reaching design load, NCO content stops heating, promptly obtaining two ends is the base polyurethane prepolymer for use as one of NCO group, its structural formula with embodiment 1, R represents diphenylmethanediisocyanate.
Behind 100g base polyurethane prepolymer for use as one and 4.9g modified silane chainextender mixing, 90 ℃ of down reactions 1 hour, promptly get to the base polyurethane prepolymer for use as two that there is the NCO group at two ends, its structural formula and with embodiment 1, wherein, R
1, R
2, R
3Represent CH
3-, C
2H
5O-or CH
3O-, R represents diphenylmethanediisocyanate.
With behind 100g base polyurethane prepolymer for use as two and the 6.3g Propylene glycol monoacrylate mixing, 80 ℃ of reactions 1 hour down, obtain silane-modified HTPB (hydroxy-terminated polybutadienes) type polyurethane acrylate, its structural formula with embodiment 1, wherein, R
1, R
2, R
3Represent CH
3-, C
2H
5O-or CH
3O-, R represents diphenylmethanediisocyanate.
Embodiment 4
Take by weighing 10g γ-An Bingjisanjiayangjiguiwan (WD-56) and join 10g γ-(2,3-epoxy third oxygen) propyl group methyl dimethoxysilane (WD-61) places there-necked flask, being warming up to 75 ℃ after mixing reacted 2 hours down, obtain containing the modified silane chainextender of secondary amino group and hydroxy functional group, its with embodiment 1;
100g HTPB is vacuumized under 110 ℃ (vacuum tightness≤-0.08MPa) 2.5 hours is to remove wherein adulterated moisture; Be cooled to 50 ℃ then, add 29g HDI, treat to be warmed up to 85 ℃ of reactions 2.5 hours after the homo(io)thermism, when reaching design load, NCO content stops heating, promptly obtaining two ends is the base polyurethane prepolymer for use as one of NCO group, its structural formula with embodiment 1, R represents hexamethylene diisocyanate.
Behind 100g base polyurethane prepolymer for use as one and 6.3g modified silane chainextender mixing, 85 ℃ of down reactions 2 hours, promptly get to the base polyurethane prepolymer for use as two that there is the NCO group at two ends, its structural formula and with embodiment 1, wherein, R
1, R
2, R
3Represent CH
3-, C
2H
5O-or CH
3O-, R represents hexamethylene diisocyanate.
With behind 100g base polyurethane prepolymer for use as two and the 6.5g Rocryl 410 mixing, 70 ℃ of reactions 2.5 hours down, obtain silane-modified HTPB (hydroxy-terminated polybutadienes) type polyurethane acrylate, its structural formula with embodiment 1, wherein, R
1, R
2, R
3Represent CH
3-, C
2H
5O-or CH
3O-, R represents hexamethylene diisocyanate.
Embodiment 5
Take by weighing 10g γ-An Bingjisanyiyangjiguiwan (KH-550) and join 11g γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (KH-560) places there-necked flask, being warming up to 70 ℃ after mixing reacted 2 hours down, obtain containing the modified silane chainextender of secondary amino group and hydroxy functional group, its with embodiment 1;
100g HTPB is vacuumized under 110 ℃ (vacuum tightness≤-0.08MPa) 2 hours is to remove wherein adulterated moisture; Be cooled to 50 ℃ then, add 28.5g IPDI, treat to be warmed up to 85 ℃ of reactions 2 hours after the homo(io)thermism, when reaching design load, NCO content stops heating, promptly obtaining two ends is the base polyurethane prepolymer for use as one of NCO group, and its structural formula and embodiment 1 are same, and R represents isophorone diisocyanate.
Behind 100g base polyurethane prepolymer for use as one and 5.2g modified silane chainextender mixing, 80 ℃ of following reactions 2.5 hours, promptly get the base polyurethane prepolymer for use as two that there is the NCO group at two ends, its structural formula and embodiment 1 are same, wherein, R
1, R
2, R
3Represent CH
3-, C
2H
5O-or CH
3O-, R represents isophorone diisocyanate.
Behind 100g base polyurethane prepolymer for use as two and 7g Hydroxyethyl acrylate mixing, 75 ℃ of following reactions 2 hours, obtain silane-modified HTPB (hydroxy-terminated polybutadienes) type polyurethane acrylate, its structural formula and embodiment 1 are same, wherein, R
1, R
2, R
3Represent CH
3-, C
2H
5O-or CH
3O-, R represents isophorone diisocyanate.
Concrete experimental example
By following test, the mechanical property and the water resistance of the light-cured resin that test the above embodiment of the present invention makes with low water absorption.
The test of experimental example 1 curing performance
The contrast test that sample and the existing ordinary light cured adhesive of embodiment 1-5 carried out mechanical property by the following method:
Method for making sample: glue is coated in two blocks of translucent sheet materials is cured;
Photocuring condition: light intensity 14mW/cm2, light application time 100s;
After fixing condition: 100 ℃ * 30min.
Experimental example 2 Mechanics Performance Testings
Hardness test: test according to GB/T 531-1999;
Tensile strength test: test according to GB/T528-1998;
Shearing resistance test: test according to GB/T7124-1986.
Test result is as shown in table 1.
Sample that table 1 embodiment 1-6 makes and ordinary light cured adhesive performance comparison test result
From The above results as can be seen, a kind of light-cured resin with low water absorption of the present invention is lower than the water-intake rate of existing ordinary light cured polyurethane acrylate resin, and its good mechanical properties, all can reach service requirements.
The above only is preferred embodiment of the present invention, and is in order to restriction the present invention, within the spirit and principles in the present invention not all, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. the light-cured resin with low water absorption is characterized in that, described light-cured resin is silane-modified hydroxy-terminated polybutadienes type polyurethane acrylate, and its structural formula is represented by following general formula (I):
Wherein: R
1, R
2, R
3Represent CH
3-, C
2H
5O-or CH
3O;
R represents tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate or hexamethylene diisocyanate.
2. the preparation method with light-cured resin of low water absorption according to claim 1 is characterized in that, wherein R
1, R
2, R
3, R definition such as in formula I definition, may further comprise the steps:
1) generate the modified silane chainextender by epoxy silane coupling and the reaction of primary amino silane coupling agent, its structural formula is represented by following general formula (II):
2) generate base polyurethane prepolymer for use as one by hydroxy-terminated polybutadienes and di-isocyanate reaction, its structural formula is represented by following general formula (III):
3) (II) formula and the reaction of (III) formula are generated base polyurethane prepolymer for use as two, its structural formula is represented by following general formula (IV):
4) (IV) formula and hydroxy acrylate reaction are generated silane-modified hydroxy-terminated polybutadienes type polyurethane acrylate.
3. the preparation method with light-cured resin of low water absorption according to claim 2, it is characterized in that, the synthesizing of modified silane chainextender in the described step 1): epoxy silane coupling is joined in the primary amino silane coupling agent, being warming up to 50～90 ℃ after mixing reacted 1～3 hour down, obtain containing the modified silane chainextender of secondary amino group and hydroxy functional group, the mol ratio of described epoxy silane coupling and primary amino silane coupling agent is 1.0～1.3: 1.
4. the preparation method with light-cured resin of low water absorption according to claim 2, it is characterized in that, described step 2) synthesizing of base polyurethane prepolymer for use as one described in: with hydroxy-terminated polybutadienes, in 100～115 ℃, vacuum tightness≤-0.08MPa, vacuumized 1.5～3 hours, and removed wherein adulterated moisture; Be cooled to 40～60 ℃ then, add vulcabond, treat to be warmed up to 70～90 ℃ of reactions 1～3 hour after the homo(io)thermism, stop heating when NCO content reaches design load, promptly getting two ends is the base polyurethane prepolymer for use as one of NCO group; The mol ratio of described vulcabond and hydroxy-terminated polybutadienes is 1.5～2.3: 1.
5. the preparation method with light-cured resin of low water absorption according to claim 2, it is characterized in that, synthesizing of base polyurethane prepolymer for use as two described in the described step 3): behind above-mentioned base polyurethane prepolymer for use as that makes one and modified silane chainextender mixing, reacted 1～3 hour down at 70～90 ℃, promptly get the base polyurethane prepolymer for use as two that there is the NCO group at two ends, the mol ratio of described modified silane chainextender and base polyurethane prepolymer for use as one is 0.1～0.3: 1.
6. the preparation method with light-cured resin of low water absorption according to claim 2, it is characterized in that, the described silane-modified hydroxy-terminated polybutadienes type polyurethane acrylate of described step 4): behind base polyurethane prepolymer for use as two and hydroxy acrylate mixing, reacted 1～3 hour down at 60～80 ℃, obtain silane-modified type polyurethane acrylate, described base polyurethane prepolymer for use as two is 0.4～0.5: 1 with the mol ratio of hydroxy acrylate.
7. the preparation method with light-cured resin of low water absorption according to claim 3, it is characterized in that, epoxy silane coupling described in the described step 1) be γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane or γ-(2,3-epoxy third oxygen) propyl group methyl dimethoxysilane.
8. the preparation method with light-cured resin of low water absorption according to claim 7, it is characterized in that the primary amino silane coupling agent described in the described step 1) is γ-An Bingjisanyiyangjiguiwan, γ-aminopropyl methyldiethoxysilane or γ-An Bingjisanjiayangjiguiwan.
9. the preparation method with light-cured resin of low water absorption according to claim 2, it is characterized in that described step 2) described in vulcabond be a kind of in tolylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate or the hexamethylene diisocyanate or several mixture arbitrarily.
10. the preparation method with light-cured resin of low water absorption according to claim 3, it is characterized in that the hydroxy acrylate described in the described step 4) is a kind of or any several mixture in Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate or the Rocryl 410.
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