CN103773305A - Preparation method of modified EPDM (Ethylene-Propylene-Diene Monomer) adhesive - Google Patents
Preparation method of modified EPDM (Ethylene-Propylene-Diene Monomer) adhesive Download PDFInfo
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- CN103773305A CN103773305A CN201310719102.4A CN201310719102A CN103773305A CN 103773305 A CN103773305 A CN 103773305A CN 201310719102 A CN201310719102 A CN 201310719102A CN 103773305 A CN103773305 A CN 103773305A
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- epdm
- preparation
- initiator
- isocyanic ester
- xylene solution
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- 229920002943 EPDM rubber Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000000853 adhesive Substances 0.000 title abstract description 7
- 230000001070 adhesive effect Effects 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 239000003999 initiator Substances 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000011230 binding agent Substances 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 14
- 239000008096 xylene Substances 0.000 claims description 14
- 150000002148 esters Chemical class 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 5
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 9
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 2
- 230000003712 anti-aging effect Effects 0.000 abstract 1
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 description 10
- 239000002184 metal Substances 0.000 description 9
- 229920001967 Metal rubber Polymers 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 230000032683 aging Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003973 paint Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- HETCEOQFVDFGSY-UHFFFAOYSA-N Isopropenyl acetate Chemical compound CC(=C)OC(C)=O HETCEOQFVDFGSY-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- -1 acrylic ester Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000013536 elastomeric material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
The invention relates to a preparation method of a modified EPDM (Ethylene-Propylene-Diene Monomer) adhesive. By using the modified EPDM adhesive, an adhered component has high peeling strength and excellent waterproof and anti-aging performances. The preparation method comprises the following steps: dissolving EPDM in a solvent, adding mixed monomers and an initiator in a certain inert atmosphere at a certain temperature, and cooling at the end of reaction; adding a certain amount of isocyanate which can be dissolved in the solvent, reacting and cooling at the end of reaction, thus obtaining the modified EPDM adhesive. The preparation method has the characteristics that the process is simple and convenient, simple equipment and easily available raw materials are used, experimental controllability is high, and the performances of the adhesive are excellent.
Description
Technical field
The invention belongs to the modified technique field of polymkeric substance, relate in particular to a kind of preparation method of modified epdm binding agent.
Background technology
Bonding science is an ancient and young subject, but until modern age, huge progress is just obtained in this field.Along with the progress of bonding science, the stress transmission of structural part prepared by bonding technology more evenly, intensity/mass ratio is higher, sealing corrosion performance better, cheaper, have comparatively ideal surface structure, easy to operate, the application of tackiness agent has been penetrated into each department in national economy, in industry, agricultural, national defence, traffic and daily life, obtain application more and more widely, become one of requisite important materials.
Non-polar material has a general problem---bad adhesion, can not effectively bond or cohesive strength is lower, the Study on Microstructure of related system and bonding process study are less, there is no the concrete bonding thinking of non-polar material, have limited development and the range of application of tackiness agent.As can be seen here, the bonding research of non-polar material is had great importance.To bonding non-polar material, mainly concentrate on and improve in cohesive strength, adopt several different methods to prepare tackiness agent, improve intensity from multiple angles.At present, patent CN1071680 discloses a kind of non-polar adhesive, the modified acrylate resin emulsion mainly forming take Vinyl Acetate Copolymer, polyvinyl acetal thing and acrylic ester emulsion is as adhesive substance, with acetone, benzene, ethanol, rosin composition solvent, and interpolation is by the mixed twine mixture of 2,4-diacetylmethane and isopropenyl acetate composition; Patent CN101643561 discloses a kind of MODIFIED PP/EPDM material adhering to and its preparation method and application that is easy to paint, PP/EPDM/M15 material surface after modification is with active carbonyl group, hydrogen and part of hydroxyl group, surface polarity increases, and makes paint be easier to adhere to.
Summary of the invention
The object of the invention is to provide in order to improve the low shortcoming of existing non-polar material cohesive strength a kind of preparation method of modified epdm binding agent, the method technique is simply controlled, can prepare high bond strength and the modified binder water-fast, ageing-resistant performance is excellent.
Technical scheme of the present invention is: the present invention designs to synthesize and utilizes solution method that monomer is introduced to EPDM by graft copolymerization, and process after modified product and obtain the binding agent that cohesive strength is high, water-fast and ageing-resistant performance is excellent by thering is the isocyanic ester of high reactivity group-NCO, and provide fundamental basis and actual application value for the bonding of non-polar material.
The concrete technical scheme of the object of the invention is: a kind of preparation method of modified epdm binding agent, and its concrete steps are as follows:
(1) under inert atmosphere protection, EPDM and dimethylbenzene are added in container, after stirring at 70～90 ℃ and being uniformly dissolved for 40～60 minutes, press initiator and EPDM mass ratio for (1～5): 1000, add the xylene solution of initiator, continue to stir that to add with EPDM mass ratio after 10～30 minutes be 1:(2～4) mix monomer, react after 5～10 hours, the reaction soln system of gained is cooled to 40～50 ℃, and wherein mix monomer is the one in the mixture of vinylformic acid and methyl methacrylate or the mixture of vinylformic acid and R 1216 acid butyl ester;
(2) press isocyanic ester and vinylformic acid mol ratio for (2～3): 1, the xylene solution of isocyanic ester is added in the reaction soln that step (1) makes, stirring reaction obtains modified epdm binding agent after 1～2 hour.
Inert atmosphere described in preferred steps (1) is the one in nitrogen or argon gas.Initiator described in preferred steps (1) is the one in benzoyl peroxide or azo-bis-isobutyl cyanide.
In mix monomer described in preferred steps (1), the mass ratio of vinylformic acid and methyl methacrylate or R 1216 acid butyl ester is (2～4): 1.
Isocyanic ester described in preferred steps (2) is isophorone diisocyanate, Toluene-2,4-diisocyanate, the one in 4-vulcabond or hexamethylene diisocyanate.
In preferred steps (1), in the xylene solution of initiator, the concentration of initiator is 0.01～0.03mol/L; In step (2), in the xylene solution of isocyanic ester, the concentration of isocyanic ester is 1～2mol/L.
In step (1), EPDM and dimethylbenzene are added in container, wherein the add-on of dimethylbenzene is for dissolving EPDM.
Modified epdm binding agent prepared by the present invention can be for the bonding of polarity and non-polar material, the especially bonding field of EPDM elastomeric material and sheet metal.It is that the stripping strength of the bonding piece of metal and EPDM rubber is 1～2MPa that the prepared modified epdm binding agent of the present invention makes matrix material.
Beneficial effect:
(1) technological process of preparing is easy, and the controllability of experiment is strong.
(2) equipment used is simple, and raw material is easy to get, with low cost, easily realizes scale production.
(3) water tolerance of bonding piece and ageing-resistant performance excellence, especially ultraviolet-resistant aging; After the uv irradiating of the water soakings of 72 hours and 356nm is processed, bonding piece is constant without breakoff phenomenon and stripping strength.
Accompanying drawing explanation
Fig. 1 is the FT-IR figure of the modified epdm binding agent paint film that makes of example 1.
Fig. 2 is that matrix material prepared by modified epdm binding agent that example 1 makes is the water resistance of the bonding piece of metal and EPDM rubber.
Fig. 3 is that matrix material prepared by modified epdm binding agent that example 1 makes is resistance to ultraviolet (356nm) aging resistance of the bonding piece of metal and EPDM rubber.
Embodiment
Example 1
(1) N
2under protection, EPDM and dimethylbenzene are added in four-hole boiling flask, after stirring at 80 ℃ and being uniformly dissolved for 40 minutes, add 0.03mol/L initiator B PO(benzoyl peroxide) xylene solution (mass ratio of benzoyl peroxide and EPDM is 1:1000), the mix monomer (wherein mix monomer is that vinylformic acid and methyl methacrylate mass ratio are 2:1) that it is 1:4 that continuation stirring added with EPDM mass ratio after 20 minutes, react after 6 hours, the reaction soln system of gained is cooled to 40 ℃;
(2) be 2.1:1 by isophorone diisocyanate and vinylformic acid mol ratio, the xylene solution of the isophorone diisocyanate of 1.5mol/L is added in the reaction soln that step (1) makes, stirring reaction obtains modified epdm binding agent after 1.5 hours.The matrix material being made by modified epdm binding agent is that the stripping strength of the bonding piece of metal and EPDM rubber is 1.3MPa.
Referring to accompanying drawing, Fig. 1 has provided the FT-IR figure of the modified epdm binding agent paint film that example 1 of the present invention makes.As can be seen from Figure 1, product is at 1712.40cm
-1near there is C=O stretching vibration, in this explanation monomer successful grafting.
Referring to accompanying drawing, it is the water resistance of the bonding piece of metal and EPDM rubber that Fig. 2 has provided matrix material prepared by modified epdm binding agent that example 1 of the present invention makes.As can be seen from Figure 2, the bonding piece excellent performance of resistance to normal-temperature water, after 72 hours water soakings, stripping strength is almost constant.
Referring to accompanying drawing, it is the ultraviolet aging resistance performance of the bonding piece of metal and EPDM rubber that Fig. 3 has provided matrix material prepared by modified epdm binding agent that example 1 of the present invention makes.As can be seen from Figure 3, the resistance to 356nm ultraviolet ray of bonding piece excellent performance, after uviolizing in 72 hours, stripping strength is almost constant.
Example 2
(1) N
2under protection, EPDM and dimethylbenzene are added in four-hole boiling flask, after stirring at 85 ℃ and being uniformly dissolved for 50 minutes, add 0.02mol/L initiator A IBN(azo-bis-isobutyl cyanide) xylene solution (mass ratio of azo-bis-isobutyl cyanide and EPDM is 3:1000), the mix monomer (wherein mix monomer is that vinylformic acid and methyl methacrylate mass ratio are 3:1) that it is 1:3 that continuation stirring added with EPDM mass ratio after 25 minutes, react after 8 hours, the reaction soln system of gained is cooled to 50 ℃;
(2) be 2.5:1 by isocyanic ester and vinylformic acid mol ratio, by the Toluene-2,4-diisocyanate of 1mol/L, the xylene solution of 4-vulcabond adds in the reaction soln that step (1) makes, and stirring reaction obtains modified epdm binding agent after 2 hours.The matrix material being made by modified epdm binding agent is that the stripping strength of the bonding piece of metal and EPDM rubber is 1.2MPa.
Example 3
(1) under argon shield, EPDM and dimethylbenzene are added in four-hole boiling flask, after stirring at 90 ℃ and being uniformly dissolved for 60 minutes, add the xylene solution (mass ratio of BPO and EPDM is 5:1000) of 0.01mol/L initiator B PO, the mix monomer that it is 1:2 that continuation stirring added with EPDM mass ratio after 30 minutes, (wherein mix monomer is that vinylformic acid and R 1216 acid butyl ester mass ratio are 4:1), reacted after 10 hours, and the reaction soln system of gained is cooled to 50 ℃;
(2) be 3:1 by isocyanic ester and vinylformic acid mol ratio, the xylene solution of the hexamethylene diisocyanate of 2mol/L is added in the reaction soln that step (1) makes, stirring reaction obtains modified epdm binding agent after 2 hours.The matrix material being made by modified epdm binding agent is that the stripping strength of the bonding piece of metal and EPDM rubber is 1.4MPa.
Claims (6)
1. a preparation method for modified epdm binding agent, its concrete steps are as follows:
(1) under inert atmosphere protection, EPDM and dimethylbenzene are added in container, after stirring at 70～90 ℃ and being uniformly dissolved for 40～60 minutes, press initiator and EPDM mass ratio for (1～5): 1000, add the xylene solution of initiator, continue to stir that to add with EPDM mass ratio after 10～30 minutes be 1:(2～4) mix monomer, react after 5～10 hours, the reaction soln system of gained is cooled to 40～50 ℃, and wherein mix monomer is the one in the mixture of vinylformic acid and methyl methacrylate or the mixture of vinylformic acid and R 1216 acid butyl ester;
(2) press isocyanic ester and vinylformic acid mol ratio for (2～3): 1, the xylene solution of isocyanic ester is added in the reaction soln that step (1) makes, stirring reaction obtains modified epdm binding agent after 1～2 hour.
2. preparation method according to claim 1, is characterized in that the inert atmosphere described in step (1) is the one in nitrogen or argon gas.
3. preparation method according to claim 1, is characterized in that the initiator described in step (1) is the one in benzoyl peroxide or azo-bis-isobutyl cyanide.
4. preparation method according to claim 1, the mass ratio that it is characterized in that vinylformic acid and methyl methacrylate or R 1216 acid butyl ester in the mix monomer described in step (1) is (2～4): 1.
5. preparation method according to claim 1, is characterized in that the isocyanic ester described in step (2) is isophorone diisocyanate, Toluene-2,4-diisocyanate, the one in 4-vulcabond or hexamethylene diisocyanate.
6. preparation method according to claim 1, is characterized in that the concentration of initiator in the xylene solution of initiator in step (1) is 0.01～0.03mol/L; In step (2), in the xylene solution of isocyanic ester, the concentration of isocyanic ester is 1～2mol/L.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01168752A (en) * | 1987-12-24 | 1989-07-04 | Mitsubishi Monsanto Chem Co | Impact-resistant resin composition |
| CN101649031A (en) * | 2009-07-17 | 2010-02-17 | 金发科技股份有限公司 | Preparation method of ethylene propylene diene monomer graft polymer and application thereof |
| CN102030866A (en) * | 2010-12-29 | 2011-04-27 | 深圳市科聚新材料有限公司 | Polybasic grafted ethylene propylene diene monomer rubber and preparation method thereof |
-
2013
- 2013-12-23 CN CN201310719102.4A patent/CN103773305B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01168752A (en) * | 1987-12-24 | 1989-07-04 | Mitsubishi Monsanto Chem Co | Impact-resistant resin composition |
| CN101649031A (en) * | 2009-07-17 | 2010-02-17 | 金发科技股份有限公司 | Preparation method of ethylene propylene diene monomer graft polymer and application thereof |
| CN102030866A (en) * | 2010-12-29 | 2011-04-27 | 深圳市科聚新材料有限公司 | Polybasic grafted ethylene propylene diene monomer rubber and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| 戴李宗: "CR/MMA-AA接枝胶粘剂的研制", 《粘合剂》, no. 3, 31 December 1990 (1990-12-31), pages 8 - 10 * |
| 滕雅娣: "EPDM-g-MMA-BA接枝聚合物胶粘剂的研制", 《橡胶工业》, vol. 51, no. 9, 31 December 2004 (2004-12-31), pages 552 - 554 * |
| 滕雅娣等: "异氰酸酯对EPDM橡胶与金属粘接性能的影响", 《材料科学与工艺》, vol. 16, no. 3, 31 December 2008 (2008-12-31), pages 423 - 426 * |
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