Summary of the invention
The object of the invention is to provide a kind of synthetic resins.
Another purpose of the present invention be to provide a kind of utilize the preparation of above-mentioned synthetic resins, have than high bond strength, better flexible ultraviolet photo-curing cementing agent.
The present invention also provides the preparation method of this ultraviolet photo-curing cementing agent.
For achieving the above object, the present invention adopts following technical scheme:
A kind of synthetic resins is made by following steps:
1. be that 189 Resins, epoxy b is heated with stirring to 100-105 ℃ with a certain amount of epoxy equivalent (weight), add successively with the b weight ratio be 18~25% hexafluoro bisphenol-a, with the b weight ratio be 0.2~0.3% quaternary ammonium salt catalyzer;
2. being warming up to 110 ℃~120 ℃ keeps more than the 20min;
3. adding and b weight ratio are 8~12% dihydroxyphenyl propane, and more than 120~127 ℃ of reaction 1.5h;
4. add the C component, described C component is made by following method: will with step 1. equally the epoxy equivalent (weight) of amount be that 149 Resins, epoxy a is heated with stirring to 100~105 ℃, add successively with a weight ratio be 25~35% dihydroxyphenyl propane, with a weight ratio be 0.1~0.2% quaternary ammonium salt catalyzer; In 115~127 ℃ react to oxirane value be termination reaction less than 0.285, be cooled to 40 ℃ promptly with bottom discharge;
5. the vinylformic acid mixed solution that contains quaternary ammonium salt catalyzer and stopper in 100~110 ℃ of droppings keeps more than the reaction 1.5h; Described quaternary ammonium salt catalyzer and b weight ratio are 0.2~0.3%, and described stopper and b weight ratio are 0.6~1%, and the weight ratio of described vinylformic acid and b is 30~40%;
6. be warming up to more than 115~127 ℃ of reaction 3.5h;
7. adding and b weight ratio are 90~120% thinner one, stir, and are cooled to 70 ℃ with bottom discharge promptly.
Described quaternary ammonium salt catalyzer is preferably Tetrabutyl amonium bromide, tetramethyl ammonium chloride, etamon chloride or 4-propyl bromide.
Described stopper is preferably MEHQ or p-ten.-butylcatechol.
Described thinner one is preferably Rocryl 410, hydroxyethyl methylacrylate, isobornyl methacrylate, stearyl methacrylate, propylene glycol diacrylate or tripropylene glycol diacrylate.
Utilize the ultraviolet photo-curing cementing agent of above-mentioned synthetic resins preparation, comprise following ingredients by weight percent:
Synthetic resins: 50~80%;
UV resin: 8~30%;
Light trigger: 2~5%;
Thixotropic agent: 1~5%;
Thinner two: 5~20%.
Described UV resin is preferably CN966J75, CN151, SR833S, CN966H90, CN9053, SR399, CN368, CN976, CN550, CN9006, CN9010, CN9008 or the CN970A60 of Sartomer company.
Described light trigger is preferably light trigger 1173,819,184, TPO, 907 or 500.
Described thixotropic agent is preferably aerosil, nano-calcium carbonate, nano zine oxide or nano aluminium oxide.
Described thinner two is Rocryl 410, hydroxyethyl methylacrylate, isobornyl methacrylate, stearyl methacrylate, propylene glycol diacrylate or tripropylene glycol diacrylate.
The preparation method of above-mentioned ultraviolet photo-curing cementing agent may further comprise the steps:
(1) preparation synthetic resins;
(2) synthetic resins, UV resin, thinner, thixotropic agent, light trigger are mixed, bottling through the whizzer deaeration, promptly gets solidified ultraviolet photo-curing cementing agent under UV-irradiation.
Light trigger 1173 is 2-hydroxy-2-methyl-1-phenyl-1-acetone; light trigger 819 is a phenyl two (2; 4; the 6-trimethylbenzoyl) phosphine oxide, light trigger 184 is 1-hydroxyl-cyclohexyl-phenyl ketone, light trigger TPO is 2; 4; 6-trimethylbenzoyl-diphenyl phosphine oxide, light trigger 907 are 2-methyl isophthalic acid-(4-methylthio group phenyl)-2-morpholinyl-1-acetone, and light trigger 500 is 50% benzophenone+50% light trigger 184.
Dihydroxyphenyl propane is 2,2-two (4-hydroxyphenyl) propane, and hexafluoro bisphenol-a is 2,2-two (4-hydroxyphenyl) HFC-236fa.
The present invention has overcome the deficiencies in the prior art, a kind of synthetic resins is provided, and utilize the preparation of this synthetic resins, have than high bond strength, better flexible ultraviolet photo-curing cementing agent, its elongation rate of tensile failure of this ultraviolet photo-curing cementing agent that makes is 20~200%, shearing resistance can reach more than the 10Mpa, can be widely used in the bonding etc. of bonding, plastics and the furniture of electron trade electronic component.Advantages such as that preparation method provided by the invention has is easy and simple to handle, mild condition.
Embodiment
The present invention is described further by the following examples, but protection scope of the present invention is not limited thereto.
Embodiment 1:
1. prepare the C component:
With 100 parts of epoxy equivalent (weight)s is that 149 Resins, epoxy a (technical grade) adds in the reaction flask, is heated with stirring to 105 ℃, add successively with a weight ratio be 33% dihydroxyphenyl propane (technical grade), with a weight ratio be 0.14% Tetrabutyl amonium bromide; In 125 ℃ of reactions, adopt hydrochloric acid acetone method (HG2-741-72) to measure its oxirane value, when oxirane value is a termination reaction less than 0.285, be cooled to below 40 ℃ promptly.
2. preparation synthetic resins:
1. be that 189 Resins, epoxy b (technical grade) is heated with stirring to 105 ℃ with 100 parts of epoxy equivalent (weight)s, add successively with the b weight ratio be 23% hexafluoro bisphenol-a (technical grade), with the b weight ratio be 0.2% Tetrabutyl amonium bromide;
2. be warming up to 120 ℃ and keep 30min;
3. adding and b weight ratio are 10% dihydroxyphenyl propane, and in 120 ℃ of reaction 2h;
4. add the C component;
5. the vinylformic acid mixed solution that contains Tetrabutyl amonium bromide, MEHQ in 110 ℃ of droppings keeps reaction 2h; The weight ratio of Tetrabutyl amonium bromide and b is 0.2%, and the weight ratio of MEHQ and b is 0.7%, and vinylformic acid (technical grade) is 35% with the weight ratio of b;
6. be warming up to 125 ℃ of reaction 4h;
7. adding with the b weight ratio is 110% hydroxyethyl methylacrylate (technical grade), stirs, and is cooled to 70 ℃ and promptly gets synthetic resins with bottom discharge;
3. preparation ultraviolet photo-curing cementing agent:
With weight percentage is that 50% synthetic resins, 30%CN966J75,5% light trigger 1173,13% hydroxyethyl methylacrylate, 2% aerosil mix, bottling, through the whizzer deaeration, promptly get solidified ultraviolet photo-curing cementing agent under UV-irradiation.
4. performance test:
Elongation rate of tensile failure is measured:
With reference to hardness rubber tensile strength and break the mensuration (GB/T1701-2001) of elongation, its elongation rate of tensile failure is 200%.
Shearing resistance is measured:
With reference to tackiness agent tensile shear strength measuring method (GB7124-1986), its shearing resistance is 12Mpa.
Embodiment 2
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??CN966J75 |
??819 |
Hydroxyethyl methylacrylate |
Aerosil |
Weight percent |
??60 |
??20 |
??2 |
??17 |
??1 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 150%.Shearing resistance is 13Mpa.
Example 3
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??CN151 |
??184 |
Hydroxyethyl methylacrylate |
Nano-calcium carbonate |
Weight percent |
??80 |
??8 |
??5 |
??5 |
??2 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 100%.Shearing resistance is 16Mpa.
Example 4
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??SR833S |
??184 |
Hydroxyethyl methylacrylate |
Nano-calcium carbonate |
Weight percent |
??70 |
??10 |
??5 |
??14 |
??1 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 120%.Shearing resistance is 15Mpa.
Example 5
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??CN966J75 |
??TPO |
Rocryl 410 |
Nano-calcium carbonate |
Weight percent |
??60 |
??10 |
??5 |
??20 |
??5 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 120%.Shearing resistance is 15Mpa.
Example 6
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??CN966H90 |
??819 |
Rocryl 410 |
Nano-calcium carbonate |
Weight percent |
??62 |
??10 |
??3 |
??20 |
??5 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 132%.Shearing resistance is 14Mpa.
Example 7
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??CN9053 |
??819 |
Hydroxyethyl methylacrylate |
Aerosil |
Weight percent |
??68 |
??20 |
??3 |
??7.5 |
??1.5 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 23%.Shearing resistance is 26Mpa.
Example 8
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??CN9053 |
??907 |
Hydroxyethyl methylacrylate |
Aerosil |
Weight percent |
??65 |
??20 |
??3 |
??10.5 |
??1.5 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 22%.Shearing resistance is 24Mpa.
Example 9
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Initiator |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??SR399 |
??907 |
Isobornyl methacrylate |
Aerosil |
Weight percent |
??73 |
??9 |
??5 |
??8 |
??5 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 37%.Shearing resistance is 20Mpa.
Example 10
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??SR399 |
??500 |
Isobornyl methacrylate |
Nano zine oxide |
Weight percent |
??60 |
??12 |
??4 |
??20 |
??4 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 50%.Shearing resistance is 19Mpa.
Example 11
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??CN368 |
??500 |
Isobornyl methacrylate |
Nano zine oxide |
Weight percent |
??54 |
??20 |
??4 |
??20 |
??2 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 31%.Shearing resistance is 20Mpa.
Example 12
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??CN368 |
??1173 |
Stearyl methacrylate |
Nano zine oxide |
Weight percent |
??63 |
??20 |
??2 |
??11 |
??4 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 29%.Shearing resistance is 22Mpa.
Example 13
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??CN976 |
??1173 |
Stearyl methacrylate |
Nano zine oxide |
Weight percent |
??70 |
??18 |
??3 |
??7 |
??2 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 21%.Shearing resistance is 27Mpa.
Example 14
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??CN550 |
??819 |
??DPGDA |
Nano zine oxide |
Weight percent |
??53 |
??28 |
??3 |
??14 |
??2 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 20%.Shearing resistance is 27Mpa.
Example 15
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??CN9006 |
??819 |
??DPGDA |
Nano zine oxide |
Weight percent |
??77 |
??8 |
??5 |
??5 |
??5 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 23%.Shearing resistance is 25Mpa.
Example 16
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??CN9010 |
??TPO |
??DPGDA |
Nano zine oxide |
Weight percent |
??68 |
??20 |
??5 |
??6 |
??1 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 31%.Shearing resistance is 21Mpa.
Example 17
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??CN9008 |
??TPO |
??TPGDA |
Nano aluminium oxide |
Weight percent |
??50 |
??27 |
??4 |
??17 |
??2 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 41%.Shearing resistance is 18Mpa.
Example 18
Preparation C component, preparation synthetic resins, preparation ultraviolet photo-curing cementing agent and performance test are with reference to embodiment 1, and wherein, each composition weight percentage composition sees the following form in the preparation preparation ultraviolet photo-curing cementing agent.
Component |
Synthetic resins |
The UV resin |
Light trigger |
Thinner |
Thixotropic agent |
The component title |
Synthetic resins |
??CN970A60 |
??TPO |
??TPGDA |
Nano aluminium oxide |
Weight percent |
??59 |
??19 |
??2 |
??17 |
??3 |
The ultraviolet photo-curing cementing agent that makes, its elongation rate of tensile failure are 37%.Shearing resistance is 20Mpa.