CN104277756A - Solvent-free synthesis method for ultra-low temperature resistant polyurethane pressure-sensitive adhesive - Google Patents
Solvent-free synthesis method for ultra-low temperature resistant polyurethane pressure-sensitive adhesive Download PDFInfo
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- CN104277756A CN104277756A CN201310279218.0A CN201310279218A CN104277756A CN 104277756 A CN104277756 A CN 104277756A CN 201310279218 A CN201310279218 A CN 201310279218A CN 104277756 A CN104277756 A CN 104277756A
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Abstract
The invention discloses a solvent-free synthesis method for an ultra-low temperature resistant polyurethane pressure-sensitive adhesive. By adopting a prepolymer method, the method includes: firstly, synthesizing an -NCO- terminated prepolymer from toluene diisocyanate (TDI) and bifunctional polyether polyol (N-220), and then mixing the prepolymer with trifunctional polyether polyol (N-330), coating release paper with the mixture, and carrying out heating curing to obtain an ultra-low temperature resistant polyurethane pressure-sensitive adhesive film. The ultra-low temperature resistant polyurethane pressure-sensitive adhesive prepared by the method provided by the invention has normal temperature bonding strength of greater than or equal to 1.0MPa (aluminum-aluminum), and -196DEG C bonding strength of greater than or equal to 13MPa (aluminum-aluminum). The adhesive is suitable for rapid bonding of parts used in an ultra-low temperature environment.
Description
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Technical field
The present invention relates to the synthetic method of polyurethane contact adhesive, in particular to a kind of solvent-free synthetic method of polyurethane contact adhesive of resistance to very low temperature.
Background technology
Pressure sensitive adhesive just refers to presser sensor, does not need heating or activating solvent, as long as by suitably pressurization, just can realize a kind of tackiness agent gluedd joint.It is due to convenient to use and used in scope widely.In cryogenic liquid storage, transport field, need a kind of pressure sensitive adhesive of resistance to very low temperature that can realize high-adhesive-strength under very low temperature.
But, although pressure sensitive adhesive is of a great variety, mainly contain the large class of acrylic acid esters co-polymer pressure sensitive adhesive, styrene-isoprene-phenylethene based block copolymer and styrene-butadiene-styrene based block copolymer pressure sensitive adhesive, Organosiliconcopolymere pressure sensitive adhesive and polyurethane contact adhesive four.In addition, polyvingl ether resene, polyisobutene class is also had, and the New Pressure-Sensitive Adhesion of some modified formation.But under ultra-low temperature surroundings, general organic adhesion agent is all converted into vitreous state and becomes fragile, and can not meet the requirement of the pressure sensitive adhesive as resistance to very low temperature.
Such as in reference 1 " development of high-low temperature resistant organic silicon pressure-sensitive adhesive ", propose a kind of method of synthesizing high-low temperature resistant organosilicon pressure pressure sensitive adhesive, it manufactures high-low temperature resistant organic pressure-sensitive gel by toluene, the vitriol oil, water glass, trimethylchlorosilane, Virahol, organo-silicone rubber, superchlorination benzoyl, dibutyl tin dilaurate.But manufactured pressure sensitive adhesive low temperature can only be applied to more than-73 DEG C, is not reported in the performance under very low temperature, have employed toluene as solvent during synthesis, not environmentally, be also unfavorable for that operator are healthy.
Such as in reference 2 " research of no-solvent type polyacrylate pressure-sensitive ", propose a kind of method manufacturing the mass polymerization of acrylate pressure-sensitive adhesive, synthesis non-solvent type acryl ester pressure-sensitive performed polymer, but acrylate pressure-sensitive adhesive is due to its molecular structure feature, only can meet the working conditions of more than-40 DEG C, not be suitable for condition of ultralow temperature.
Reference
Reference 1: Guo Jinyan, Di Mingwei, Zhang Entian etc. the development of high-low temperature resistant organic silicon pressure-sensitive adhesive. Chinese tackiness agent, 2003,12(5): 23-28
Reference 2: Chen Rongzhen. the research of no-solvent type polyacrylate pressure-sensitive. East China University of Science, 2006 postgraduate's master thesis
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of no-solvent synthesis process of the pressure sensitive adhesive of resistance to ultra-low temperature polyurethane.
The uninanned platform technical process of the pressure sensitive adhesive of resistance to ultra-low temperature polyurethane provided by the invention is as follows:
(1) polyether polyols dehydration of alcohols: using as two functional polyethers polyvalent alcohol N-220 of polyether glycol and trifunctional polyether glycol N-330 thermal dehydration;
(2) synthesis of-NCO base performed polymer is held: in two functional polyethers polyvalent alcohol N-220, add tolylene diisocyanate TDI while stirring, in dropping process, keep temperature of reaction below 40 DEG C, after adding described tolylene diisocyanate TDI, oil bath is heated to 75 ± 5 DEG C and carries out back flow reaction, obtains end-NCO base performed polymer;
(3) pressure sensitive adhesive synthesis: in gained end-NCO base performed polymer, add trifunctional polyether glycol N-330 and mix, then mixture being coated on interleaving paper, being heating and curing and obtaining pressure sensitive adhesive.
The invention has the beneficial effects as follows:
(1) building-up process of this pressure sensitive adhesive of resistance to ultra-low temperature polyurethane is solvent-free, is conducive to the health of environmental protection and producers.
(2) pressure sensitive adhesive that this pressure sensitive adhesive of resistance to ultra-low temperature polyurethane obtains not only has good bonding strength at normal temperatures, and has higher bonding strength under very low temperature.
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Accompanying drawing explanation
Fig. 1, Fig. 2 are N-220, N-330 dewatering unit schematic diagram and TDI and N-220 prepolymerization reaction device schematic diagram in the present invention respectively.
Wherein: 1-heating-type magnetic stirrer; 2-oil bath pan; 3-there-necked flask; 4-glass stopper; 5-rubber plug; 6-thermometer; 7-adapter; 8-rubber rising pipe; 9-condenser; 10-rubber water inlet pipe; 11-Erlenmeyer flask; 12-spherical hopper.
Fig. 3 is the reaction formula that in the present invention, TDI and N-220 reaction generates performed polymer.
Fig. 4 is the performed polymer and N-330 crosslinking reaction formula that in the present invention, TDI and N-220 reaction generates.
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Embodiment
Below in conjunction with accompanying drawing and concrete embodiment, set forth the present invention further.These embodiments are interpreted as only being not used in for illustration of the present invention limiting the scope of the invention.After the content of having read the present invention's record, those skilled in the art can make various changes or modifications the present invention, and these equivalence changes and modification fall into the scope of the claims in the present invention equally.
The no-solvent synthesis process of the pressure sensitive adhesive of resistance to ultra-low temperature polyurethane of the present invention, it, under adopting prepolymer method first to synthesize the condition of end-NCO base performed polymer, adds trifunctional polyether glycol and is heating and curing and can obtains the pressure sensitive adhesive of resistance to ultra-low temperature polyurethane.
In this manual, two described functional polyethers polyvalent alcohol N-220 are sometimes referred to as N-220, and it is: the polyether polyol of two functional group's relative molecular masses 2000, and hydroxyl value is 53.0 ~ 56.0KOHmg/g; Described trifunctional polyether glycol N-330 is sometimes referred to as N-330, and it is: the polyether polyol of trifunctional relative molecular mass 3000, and hydroxyl value is 53.0 ~ 56.0KOHmg/g.
Two functional polyethers polyvalent alcohol N-220, trifunctional polyether glycol N-330 are the commercially available prod of Nanjing petrochemical industry two factory.
Below preparation method of the present invention is described in detail.
(1) polyether polyols dehydration of alcohols:
Such as shown in Figure 1, in there-necked flask 3, add N-220, the rubber plug 5 being inserted with thermometer 6 is loaded the middle port place of there-necked flask 3, with glass stopper 4, side mouth is clogged, there-necked flask 3 is fixed, and place heating-type magnetic stirrer 1, oil bath pan 2 successively under flask 3 after three.Then at another side mouth of there-necked flask 3, adapter 7 being installed, being then connected being equipped with rubber rising pipe 8 with adapter 7 with the prolong 9 of rubber water inlet pipe 10, after having connected, Erlenmeyer flask 11 is placed in immediately below prolong outlet.
After all devices has connected, open heating-type magnetic stirrer 1, heat while stirring, oil bath pan 2 heating is carried out processed to N-220 or N-330.Herein, processed temperature is generally 120 ± 5 DEG C.Dehydration temperaturre is too high, likely produces by product.Dehydration temperaturre is too low, likely can not reach the effect of dehydration.In addition, for dehydration treatment time, as long as the time of dehydrating function can be completed, be just not particularly limited.In order to ensure abundant dehydration, be that under the condition of 120 ± 5 DEG C, dewatering time is preferably 3 ± 0.5h in processed temperature.Dewatering time is greater than 3.5h, and by product may be caused to produce, and is not suitable for from time and economic angle.Dewatering time is less than 2.5h, likely dewaters insufficient.
After the dehydration is completed, close the heating function of heating-type magnetic stirrer 1, still the material temperature be stirred in there-necked flask 3 is down to room temperature, remove prolong 9, adapter 7, heating-type magnetic stirrer 1, oil bath pan 2, rubber plug 5, thermometer 6, glass stopper 4, N-220 or N-330 in there-necked flask 3 is poured out, bottle to seal and preserve.
(2) synthesis of-NCO base performed polymer is held:
As shown in Figure 2, the N-220 of dehydration is added in there-necked flask 3, the rubber plug 5 being inserted with thermometer 6 is loaded a side Kou Chu of there-necked flask 3, there-necked flask 3 is fixed, in middle port, the prolong 9 of rubber rising pipe 8 and rubber water inlet pipe 10 be installed and fix prolong 9.Then in the spherical hopper 12 of rubber plug 5, add TDI, load another side mouth of there-necked flask 3.
After all devices has connected, open heating-type magnetic stirrer 1, heat while stirring, meanwhile, after starting stirring, open the valve of spherical hopper 12, be added dropwise to by TDI in there-necked flask 3 and react with N-220, control temperature is below 40 DEG C.Herein, temperature is comparatively crucial.If temperature is higher than 40 DEG C, then easily sudden and violent poly-, this is because the polyreaction of isocyanic ester and alcoholic extract hydroxyl group is thermopositive reaction.
After TDI dropwises, oil bath pan 2 is adopted to heat up, temperature of reaction is made to remain on 75 ± 5 DEG C, more than back flow reaction 3h, after the prepolymerization reaction of TDI and N-220 completes, material temperature is down to room temperature, remove prolong 9, heating-type magnetic stirrer 1, oil bath pan 2, rubber plug 5, thermometer 6, spherical hopper 12, the performed polymer in there-necked flask 3 is poured out, bottle to seal and preserve.Herein, temperature of reaction is comparatively crucial.If temperature of reaction is higher than 80 DEG C, then easily sudden and violent poly-.If temperature of reaction is lower than 70 DEG C, then the reaction times is longer.About the time of back flow reaction, be just not particularly limited as long as fully proceed to the time till terminating of reacting.In order to ensure sufficient reacting, be generally more than 3 hours.
Its reaction formula as shown in Figure 3.
In addition, in the synthesis of this end-NCO base performed polymer, the proportioning of described tolylene diisocyanate TDI and two functional polyethers polyvalent alcohol N-220 can be TDI/N-220=5/2 ~ 5/1(mol ratio).
(3) pressure sensitive adhesive synthesis:
The reaction formula of this step as shown in Figure 4.
After performed polymer prepares, according in performed polymer-content of NCO group, proportionally add N-330.Such as when TDI/N-220=5/2 ~ 5/1, can according to performed polymer/N-330=1/1 ~ 1/2(mass ratio) ratio, weigh performed polymer, N-330 respectively, it is mixed in glass cylinder, be coated on interleaving paper, blade coating is even, then puts into curing oven, can obtain the pressure sensitive adhesive of resistance to ultra-low temperature polyurethane.
Herein, solidification is had no particular limits.As long as the condition that can solidify.Such as can put into curing oven and solidify 1h at 100 ± 5 DEG C.
Embodiment
The mensuration of bonding strength:
According to " pressure-sensitive adhesive tape shear strength test method GB7754-87 " standard, bonding strength test is carried out to the pressure sensitive adhesive obtained in examples and comparative examples of the present invention, and adopts aluminium-aluminium bonding test piece test tensile-sbear strength to characterize the bonding strength of this tackiness agent.Test process is as follows: on the aluminium alloy test plate (panel) of 10 groups of wide 20mm, long 300mm, adhesive coating mixture makes test sample, tensile-sbear strength test is carried out respectively at normal temperature and-196 DEG C, test environment humidity 45% ~ 55%, trier chuck translational speed 300 ± 30mm/min.
Embodiment 1:
(1) polyether polyols dehydration of alcohols:
In there-necked flask 3, put into polyether glycol N-220 or polyether glycol N-330, linking device, heats while stirring, oil bath pan 2 is heated to 120 ± 5 DEG C and carries out processed 3h to N-220 or N-330.
(2) synthesis of-NCO base performed polymer is held:
In there-necked flask 3, add the polyether glycol N-220 of dehydration, linking device, heats while stirring, and be added dropwise to by TDI in there-necked flask 3 and react with polyether glycol N-220, control temperature is at 40 DEG C.After TDI dropwises, adopt oil bath pan 2 to heat up, make temperature of reaction remain on 75 DEG C, after the prepolymerization reaction of back flow reaction 3h, TDI and N-220 completes, material temperature is down to room temperature.
In addition, in the synthesis of this end-NCO base performed polymer, the proportioning of described tolylene diisocyanate TDI and two functional polyethers polyvalent alcohol N-220 is TDI/N-220=5/2(mol ratio).
(3) pressure sensitive adhesive synthesis:
After performed polymer prepares, according to performed polymer/N-330=1/2(mol ratio) ratio, weigh performed polymer, N-330 respectively, it is mixed in glass cylinder, be coated on interleaving paper, blade coating is even, then puts into baking oven and solidify 1h at 100 ± 5 DEG C, the pressure sensitive adhesive of the resistance to ultra-low temperature polyurethane A1 in obtained the present invention.
Pressure sensitive adhesive A1, during normal temperature, bonding strength is 1.1MPa(aluminium-aluminium), when-196 DEG C, bonding strength is 13MPa(aluminium-aluminium).
Embodiment 2:
Except being set to except 35 DEG C by temperature when TDI drips in (2) end-NCO base performed polymer synthesis in embodiment 1, other carries out similarly to Example 1, obtains polyurethane contact adhesive A2.
Pressure sensitive adhesive A2, during normal temperature, bonding strength is 1.0MPa(aluminium-aluminium), when-196 DEG C, bonding strength is 13MPa(aluminium-aluminium).
Embodiment 3:
Except the ratio of performed polymer/N-330 in (3) pressure sensitive adhesive synthesis in embodiment 1 is set to=1/1(mol ratio) except, other carries out similarly to Example 1, obtains polyurethane contact adhesive A3.
Pressure sensitive adhesive A3, during normal temperature, bonding strength is 0.3MPa(aluminium-aluminium), when-196 DEG C, bonding strength is 1MPa(aluminium-aluminium).
Embodiment 4:
Except the ratio of performed polymer/N-330 in (3) pressure sensitive adhesive synthesis in embodiment 1 is set to=3/1(mol ratio) except, other carries out similarly to Example 1, obtains polyurethane contact adhesive A4.
Pressure sensitive adhesive A4, during normal temperature, bonding strength is 0.7MPa(aluminium-aluminium), when-196 DEG C, bonding strength is 5MPa(aluminium-aluminium).
Comparative example 1:
Except being set to except 45 DEG C by temperature when TDI drips in (2) end-NCO base performed polymer synthesis in embodiment 1, other carries out similarly to Example 1, obtains polyurethane contact adhesive B1.
Pressure sensitive adhesive B1, during normal temperature, bonding strength is 0.8MPa(aluminium-aluminium), when-196 DEG C, bonding strength is 6.0MPa(aluminium-aluminium).
Comparative example 2:
Except being set to except 85 DEG C by temperature of reaction in (2) end-NCO base performed polymer synthesis in embodiment 1, other carries out similarly to Example 1, obtains polyurethane contact adhesive B2.
Pressure sensitive adhesive B2, during normal temperature, bonding strength is 0.4MPa(aluminium-aluminium), when-196 DEG C, bonding strength is 2MPa(aluminium-aluminium).
Comparative example 3:
Except being set to except 65 DEG C by temperature of reaction in (2) end-NCO base performed polymer synthesis in embodiment 1, other carries out similarly to Example 1, obtains polyurethane contact adhesive B3.
Pressure sensitive adhesive B3, during normal temperature, bonding strength is 1.1MPa(aluminium-aluminium), when-196 DEG C, bonding strength is 13MPa(aluminium-aluminium).
As can be seen from embodiment and comparative example: in embodiment 1 ~ 3, pressure sensitive adhesive A1, A2 of prepared in accordance with the method for the present invention, bonding strength >=1.0MPa(aluminium-aluminium during normal temperature), bonding strength >=13MPa(aluminium-aluminium when-196 DEG C) and, obtain good effect.
In comparative example 1, because temperature when dripping TDI is too high, difficult control of temperature in dropping process, reaction is violent, and local reaction is difficult to control, and the performed polymer range of molecular weight distributions of formation is wider, and bonding strength is lower.
In comparative example 2, because in the synthesis of end-NCO base performed polymer, temperature of reaction is too high, easily sudden and violent poly-in performed polymer building-up process, cause bonding strength very low.
In comparative example 3, because in the synthesis of end-NCO base performed polymer, temperature of reaction is too low, performed polymer building-up reactions is comparatively slow, and process is longer, but the bonding strength of pressure sensitive adhesive is unchanged.
The uninanned platform technical maturity of the pressure sensitive adhesive of resistance to very low temperature using equipment and process described in the present embodiment to prepare, stable, technological process is simple to operation, pressure sensitive adhesive normal temperature, very low temperature adhesiveproperties are good, use the rapid link of part under being applicable to ultra-low temperature surroundings.
Claims (5)
1. a no-solvent synthesis process for the pressure sensitive adhesive of resistance to ultra-low temperature polyurethane, is characterized in that, it comprises the steps:
(1) polyether polyols dehydration of alcohols: using as two functional polyethers polyvalent alcohol N-220 of polyether glycol and trifunctional polyether glycol N-330 thermal dehydration;
(2) synthesis of-NCO base performed polymer is held: in two functional polyethers polyvalent alcohol N-220, add tolylene diisocyanate TDI while stirring, in dropping process, keep temperature of reaction below 40 DEG C, after adding described tolylene diisocyanate TDI, oil bath is heated to 75 ± 5 DEG C and carries out back flow reaction, obtains end-NCO base performed polymer;
(3) pressure sensitive adhesive synthesis: in gained end-NCO base performed polymer, add trifunctional polyether glycol N-330 and mix, then mixture being coated on interleaving paper, being heating and curing and obtaining pressure sensitive adhesive.
2. synthetic method as claimed in claim 1, it is characterized in that: in described end-NCO base performed polymer synthesis, be TDI/N-220=5/2 ~ 5/1(mol ratio in the proportioning of described tolylene diisocyanate TDI and two functional polyethers polyvalent alcohol N-220) time, in described pressure sensitive adhesive synthesis, the proportioning of described end-NCO base performed polymer and trifunctional polyether glycol N-330 is for holding-NCO base performed polymer/N-330=1/2 ~ 3/1(mol ratio).
3. synthetic method as claimed in claim 1 or 2, is characterized in that: in described polyether polyols dehydration of alcohols, and in described step (1), thermal dehydration is thermal dehydration 3 ± 0.5h under 120 ± 5 DEG C of conditions.
4. synthetic method as claimed in claim 1 or 2, is characterized in that: in described end-NCO base performed polymer synthesis, in described step (2), back flow reaction carries out more than 3 hours.
5. synthetic method as claimed in claim 1 or 2, is characterized in that: in described pressure sensitive adhesive synthesis, be heating and curing as solidifying 1h at 100 ± 5 DEG C in described step (3).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110373147A (en) * | 2019-08-01 | 2019-10-25 | 荆晓东 | A kind of high-weathering-resistance polyurethane adhesive and preparation method thereof |
| CN111234766A (en) * | 2020-03-17 | 2020-06-05 | 北京华腾新材料股份有限公司 | Ultralow-temperature and cold-heat impact resistant two-component polyurethane adhesive and preparation method thereof |
| CN113401520A (en) * | 2021-04-06 | 2021-09-17 | 巢进化学(上海)有限公司 | Application of PSA (pressure swing adsorption) in refrigerated container |
| CN117050712A (en) * | 2023-07-27 | 2023-11-14 | 广东中粘新材料科技有限公司 | Low-temperature-resistant solvent-free polyurethane adhesive |
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2013
- 2013-07-04 CN CN201310279218.0A patent/CN104277756A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110373147A (en) * | 2019-08-01 | 2019-10-25 | 荆晓东 | A kind of high-weathering-resistance polyurethane adhesive and preparation method thereof |
| CN111234766A (en) * | 2020-03-17 | 2020-06-05 | 北京华腾新材料股份有限公司 | Ultralow-temperature and cold-heat impact resistant two-component polyurethane adhesive and preparation method thereof |
| CN111234766B (en) * | 2020-03-17 | 2023-03-28 | 北京华腾新材料股份有限公司 | Ultralow-temperature and cold-heat impact resistant two-component polyurethane adhesive and preparation method thereof |
| CN113401520A (en) * | 2021-04-06 | 2021-09-17 | 巢进化学(上海)有限公司 | Application of PSA (pressure swing adsorption) in refrigerated container |
| CN113401520B (en) * | 2021-04-06 | 2022-07-26 | 巢进化学(上海)有限公司 | Application of PSA in refrigerated container |
| CN117050712A (en) * | 2023-07-27 | 2023-11-14 | 广东中粘新材料科技有限公司 | Low-temperature-resistant solvent-free polyurethane adhesive |
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Application publication date: 20150114 |