CN1705727A - Process for producing chloroprene-based graft adhesive - Google Patents
Process for producing chloroprene-based graft adhesive Download PDFInfo
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- CN1705727A CN1705727A CN 200480001352 CN200480001352A CN1705727A CN 1705727 A CN1705727 A CN 1705727A CN 200480001352 CN200480001352 CN 200480001352 CN 200480001352 A CN200480001352 A CN 200480001352A CN 1705727 A CN1705727 A CN 1705727A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
- C09J151/04—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to rubbers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F279/00—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00
- C08F279/02—Macromolecular compounds obtained by polymerising monomers on to polymers of monomers having two or more carbon-to-carbon double bonds as defined in group C08F36/00 on to polymers of conjugated dienes
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Abstract
A process for producing a chloroprene-based graft adhesive which has a regulated rate of organic-solvent volatilization. The process, which is for producing a chloroprene-based graft adhesive by graft-polymerizing methyl methacrylate with polychloroprene, is characterized in that the graft polymerization of methyl methacrylate with polychloroprene is conducted in an organic solvent (A) alone or a mixed solvent comprising the organic solvent (A), the solvent (A) and the mixed solvent being capable of dissolving the polychloroprene therein and having a boiling point or azeotropic point higher than 70 DEG C, and other organic solvent (B) alone or a mixed solvent containing the organic solvent (B) is added to the resultant reaction mixture.
Description
Technical field
The present invention relates to the preparation method of the evaporation rate of organic solvent through the chloroprene based graft adhesive of adjustment.
Background technology
It is the tackiness agent use of the difficult jointing material of representative that sovprene and methyl methacrylate-grafted polymeric chloroprene based graft adhesive are suitable as with synthetic leather, plastic material etc., particularly is widely used in (for example with reference to non-patent literatures 1 and 2) such as shoe industry and case and bag production.
But, among the preparation method in the past,, must carry out graft polymerization at 70～90 ℃ in order to control the percent polymerization of methyl methacrylate (hereinafter referred to as MMA), because the relation of azeotropic point, the solvent composition that can be used for graft polymerization is restricted.Therefore, the evaporation rate of the solvent of gained graft adhesive also will inevitably be restricted.
Non-patent literature 1: adherent technology Vol.21, total the 65th phase of No.4 (2002) (page 4,1.3 (2), the 2nd paragraph)
Non-patent literature 2: the Japanese bonding will Vol.20 of association, No.6 (1984) (the 34th page)
The announcement of invention
The objective of the invention is to pass through chloroprene based graft adhesive of adjusting and preparation method thereof in view of present situation provides the evaporation rate of organic solvent.
Among the present invention, when preparation makes the chloroprene based graft adhesive of sovprene and methacrylic acid graft polymerization, by in solubilized sovprene and boiling point or azeotropic point more than 70 ℃, better be in the independent organic solvent A more than 80 ℃ or contain in the mixed solvent of organic solvent orange 2 A, after making sovprene and methyl methacrylate carry out graft polymerization, add another organic solvent B more separately or contain the mixed solvent of organic solvent B and prepare the chloroprene based graft adhesive, can regulate the evaporation rate of organic solvent, thereby finish the present invention.
Therefore, the present invention has following technical essential.
(1) preparation method of chloroprene based graft adhesive, the feature of this method is, when preparation makes sovprene and methyl methacrylate-grafted polymeric chloroprene based graft adhesive, be higher than 70 ℃ independent organic solvent A or contain in the mixed solvent of organic solvent orange 2 A in solubilized sovprene and boiling point or azeotropic point, after making sovprene and methyl methacrylate carry out graft polymerization, add another organic solvent B more separately or contain the mixed solvent of organic solvent B.
(2) preparation method of chloroprene based graft adhesive of (1) record, independent organic solvent A contain the boiling point of mixed solvent of organic solvent orange 2 A or azeotropic point more than 80 ℃.
(3) preparation method of the chloroprene based graft adhesive of (1) or (2) record, the amount of the organic solvent A when being used for graft polymerization is 50～80 quality % of organic solvent total amount, and the amount of the organic solvent B that adds after graft polymerization is 50～20 quality %.
(4) preparation method of the chloroprene based graft adhesive of each record in (1)～(3), the solid formation of the sovprene before the graft copolymerization divides more than 15%.
(5) preparation method of the chloroprene based graft adhesive of each record in (1)～(4), 100 ℃ of mooney viscosity MS (2+2.5) that are used for the sovprene of graft polymerization are below 40 or the viscosity of 20 ℃ 10% toluene solution is below the 400mPas.
(6) preparation method of the chloroprene based graft adhesive of each record in (1)～(5), the organic solvent A of the solvent during as graft polymerization is the mixed solvent that contains toluene and ethyl methyl ketone.
(7) the chloroprene based graft adhesive that makes of the preparation method by the chloroprene based graft adhesive of each record in (1)～(6), its viscosity is 1000～5000mPas, is divided into 12～22% Gu form.
The chloroprene based graft adhesive is owing to be subjected to the restriction of graft polymerization temperature, and spendable organic solvent is more limited, is difficult to control rate of drying.The evaporation rate that utilizes the present invention can obtain organic solvent has passed through the chloroprene based graft adhesive of adjusting.
The best mode that carries out an invention
Sovprene of the present invention (below be also referred to as CR) be meant the homopolymer of chlorbutadiene (hereinafter referred to as chloroprene) or chloroprene and can with the monomeric interpolymer of chloroprene copolymerization.
Among the present invention, can use in homopolymer and the interpolymer any, but consider, be more preferably and adopt the chloroprene homopolymer from bond strength.
Here, can can exemplify 2 with the monomer of chloroprene copolymerization, 3-two chloro-1,3-butadienes, 1-chloro-1,3-divinyl, divinyl, isoprene, vinylbenzene, vinyl cyanide, vinylformic acid or its ester class, methacrylic acid or its ester class etc. also can be used more than 2 kinds as required.
CR structure of the present invention is not particularly limited, can molecular weight, molecular weight distribution, molecular end structure and crystallization velocity etc. be adjusted by suitably selecting and controlled polymerization temperature, polymerization starter, chain-transfer agent, short-stopper, final percent polymerization etc.Consider that from bonding rerum natura crystallization velocity is suitable fast.
Based on reason described later, the molecular weight of CR is suitable little, and mooney viscosity (100 ℃ of MS (2+2.5)) is more preferably mooney viscosity in 15～35 scope below 40.Perhaps, 20 ℃ 10% toluene solution viscosity below 400mPas better is below 300mPas.
When preparing chloroprene based graft adhesive of the present invention, CR is dissolved in the organic solvent A, in this system, makes methyl methacrylate (below be also referred to as MMA) and CR graft polymerization.
At this moment, the addition of MMA is not particularly limited, corresponding to the CR of 100 mass parts, MMA is preferably 10～100 mass parts, and more preferably 30～70 mass parts are preferably 50～65 mass parts.
The graft polymerization of MMA can be implemented according to ordinary method.Can select according to solubleness, the graft polymerization temperature of CR as the organic solvent A that is used for the polymeric solvent, but this organic solvent A and the boiling point or the azeotropic point that contain the mixed solvent of organic solvent orange 2 A must be higher than 70 ℃, be more preferably more than 80 ℃, when boiling point or azeotropic point when the solvent boiling takes place below 70 ℃, obviously be difficult to the MMA transformation efficiency of graft polymerization is controlled in the purpose scope.
As used organic solvent A, can use aromatic solvents such as toluene, dimethylbenzene, heptane, octane, hexanaphthene, methylcyclohexane saturated hydrocarbons such as (MCH), ethyl methyl ketone (hereinafter referred to as MEK), ethyl acetate isopolarity solvent generally can suitably mix them and use.
Consider that from the angle of controlled polymerization temperature best is the combination of toluene and MEK, the volume ratio of toluene/MEK is preferably 95/5～20/80, and good especially is 70/30～30/70.
The organic solvent A that is used for graft polymerization or the amount of its mixed solvent are not particularly limited, if the amount of the organic solvent B of considering to add after the solid formation branch of product and the polymerization (below be also referred to as diluting solvent), then to be advisable less as much as possible, corresponding to used organic solvent total amount (the total amount of organic solvent A and organic solvent B), be preferably 50～80 quality %.
If exemplify object lesson, then corresponding to the CR of 100 mass parts, organic solvent A is preferably about 200～500 mass parts, more preferably 300～400 mass parts.It better is to be adjusted into more than 15% that the solid formation of CR before the graft copolymerization in the organic solvent A divides, and is more preferably to be adjusted into more than 17%.
If the amount of organic solvent A is (the solid formation of CR divides very few) too much, then product viscosity is low excessively, perhaps organic solvent B (diluting solvent) amount must be controlled to be on a small quantity, so just is difficult to carry out the adjusting of the evaporation rate of the solvent in the chloroprene-based tackiness agent.
The amount of organic solvent A very few if (the solid formation of CR divides too much), then the viscosity of solution is too high, not only is difficult to carry out the temperature control of graft polymerization, also can increase the load of device, consequently, is difficult to graft polymerization is controlled.
During graft polymerization, the viscosity of raw materials used CR also is the adjusting generation considerable influence of soltion viscosity to polymerization.Therefore, as mentioned above, preferably adopt the low CR of viscosity.
Graft polymerization temperature to MMA is not particularly limited, but for polyreaction is carried out smoothly, this temperature is preferably 70～90 ℃, more preferably 80～90 ℃.
Polymerization starter is not particularly limited, can adopts with benzoyl peroxide (hereinafter referred to as BPO) to be the organo-peroxide of representative, to be azo-compound of representative etc. with the Diisopropyl azodicarboxylate.In order to improve the graft reaction rate, be preferably the employing organo-peroxide, consider from the angle of polymerization control, preferably use BPO.
Consider that from the processing difficulty of superoxide and the complexity of polymerization control the optimal BPO of being to use carries out polymerization at 80～85 ℃.
Percent polymerization (transformation efficiency that the MMA monomer transforms to the MMA polymkeric substance) to the MMA graft polymerization is not particularly limited, and considers from bond strength, is preferably 30～60%.More preferably 40～50%.
Can utilize short-stopper to stop grafting and engage, used short-stopper is not particularly limited, can adopt general short-stopper with percent polymerization arbitrarily.Specifically can exemplify quinhydrones, 2, the 6-tertiary butyl-4-methylphenol (hereinafter referred to as BHT), thiodiphenylamine, azanol etc.
After the MMA graft reaction finishes, in graft polymerization liquid, add another organic solvent B different, regulate the evaporation rate of the organic solvent in the final tackiness agent with organic solvent A.The organic solvent B that added this moment is not particularly limited, and also can select organic solvent B according to the purpose evaporation rate of MMA graft polymerization liquid.
Relative velocity of evaporation when general known solvent is benchmark with the n-butyl acetate (for example, bonding big encyclopaedia (1993) is towards (the 215th page in storehouse bookstore periodical, table 15.13)), for the such mixed solvent system of chloroprene based graft adhesive of the present invention, can extrapolate its velocity of evaporation according to the numerical value of each organic solvent.
In addition, the secondary effect of utilizing method of the present invention to prepare graft adhesive is to adjust the content of hazardous property solvents such as aromatic solvent.
When slowing down the rate of drying of chloroprene based graft adhesive, as organic solvent B, better be relative velocity of evaporation at the organic solvent below 240, good especially is that this speed is at the organic solvent below 100.Its object lesson comprises octane, toluene, dimethylbenzene, Lay, chlorobenzene, naphthane, tetrachloroethane, diisobutyl ketone, propyl acetone, butyl propionate, pimelinketone, cyclopentanone, butylacetate, N, dinethylformamide and their mixed solvent etc.
In addition, as the organic solvent B of the rate of drying of accelerating the chloroprene based graft adhesive, better be relative velocity of evaporation at the organic solvent more than 250, good especially is that this speed is at the organic solvent more than 500.Its object lesson comprises pentane, hexane, hexanaphthene, heptane, methylcyclohexane, the industrial gasoline of lower boiling, acetone, ethyl methyl ketone, ethyl acetate, propyl acetate, ether, tetrahydrofuran (THF), methylene dichloride, chloroform, tetracol phenixin and their mixed solvent etc.
Like this, utilize the present invention can obtain to have that viscosity is preferably 1000～5000mPas, particularly preferably 1500～4000mPas, solid formation are divided the chloroprene based graft adhesive that is preferably 12～22%, particularly preferably 15～20% good characteristic.
Utilize chloroprene based graft adhesive that the present invention obtains when reality is used, for characteristics such as its initial stage bounding force of balance, water-resistant bonding power, bonding hold-times and more tend to practicability, preferably add tackifying resin.
When mixing tackifying resin, its kind is not particularly limited, specifically can exemplifies Gum Rosin, polymerized rosin resin, α-Pai Xishuzhi, beta-pinene resin, terpene-phenolic resin, C 5 fraction through-stone oleo-resinous, C9 cut through-stone oleo-resinous, C5/C9 cut through-stone oleo-resinous, DCPD through-stone oleo-resinous, alkyl phenol resin, xylene resin, coumarone resin, coumarone-indene resin etc.Consider from bonding physical properties balance such as bond strength, serviceable time, binding property, preferably use terpene-phenolic resin.
The chloroprene based graft adhesive that the present invention obtains in order to realize desired performance, also can add solidifying agent, metal oxide, weighting agent, UV light absorber, oxidation inhibitor, silane coupling agent and chlorinatedpolyethylene etc. arbitrarily except above-mentioned.
Particularly also favourable for increasing substantially bond strength with solidifying agent, therefore recommend energetically.In this case, form 2 liquid type tackiness agents, owing to the viscosity behind the common interpolation solidifying agent can rise, so the serviceable time is restricted.Therefore, solidifying agent should will used preceding interpolation at once.
Embodiment
Below, by embodiment and comparative example the present invention and effect thereof are elaborated, but these embodiment can't limit the present invention.In the following description, as be not particularly limited, part and % are quality criteria.
Embodiment 1
In the glass reactor of agitating wing and condenser is housed, CR (1/1 melange, the A-30:MS (2+2.5) 100 ℃=20 of electrochemical industry A-30/A-70, A-70:MS (2+2.5) 100 ℃=40) is dissolved among the mixed organic solvents A of 150 parts of toluene and 250 parts of MEK for 100 parts.Then, add 60 parts of MMA, in air atmosphere, temperature is remained on 80 ℃.
The solid formation that utilizes formula (several 1) to calculate the preceding CR of graft copolymerization is divided into 17.86%.
[several 1]
Divide (%)=CR consumption (mass parts)/(amount of organic solvent A (mass parts)+MMA consumption (mass parts)) * 100 Gu form
Then, add 0.6 part of BPO, when stirring, begin graft polymerization reaction as polymerization starter.The BHT that adds 2.0 parts after reacting 5 hours stops polymerization, obtains chloroprene-based graft reaction liquid.The transformation efficiency of the MMA of the chloroprene-based graft reaction liquid of gained is 45%, is divided into 22.8% Gu form.
In addition, with Kreuk Field rotary type viscometer, recording 25 ℃ of the chloroprene-based graft reaction liquid of gained, the viscosity of 12rpm is 14500mPas.
The viscosity of 20 ℃ 10% toluene solution of the CR of present embodiment is 250mPas.
In the chloroprene-based graft reaction liquid of gained, add as 200 parts of the hexanaphthenes of organic solvent B (diluting solvent), obtain the chloroprene based graft adhesive that evaporation rate is accelerated to some extent.
Gained chloroprene based graft adhesive is implemented the evaporation rate test of machine solvent.The 4g tackiness agent extended on teflon system flap is the circle of diameter 6cm, and the weight of measuring respectively at regular intervals under 23 ℃, humidity 70% atmosphere reduces.Obtain the 50% evaporable time that forms the organic solvent amount of branch reckoning from solid by measurement result, carry out the comparison of evaporation rate.
Then, in this graft adhesive, add 3 parts of デ ス モ ジ ュ-Le RFE (Bayer corporate system, polyisocyanate curing agent divide 27% Gu form), behind the thorough mixing, with 200g/cm as solidifying agent
2It is coated 2 PCV synthetic leather sheets (60% area (25 * 60mm) of the one side of 25mm * 100mm).After dry 30 minutes, the split leather corium, maintenance was measured normality intensity after 7 days.
Utilize tensile testing machine, in 23 ℃ atmosphere, with the draw speed of 50mm/min measure T type stripping strength with this as normality intensity.
Embodiment 2
Add in the chloroprene-based then reaction solution that embodiment 1 obtains that (100 parts of 100 parts of octanes of diluting solvent and dimethylbenzene obtain the chloroprene based graft adhesive that evaporation rate has slowed down as organic solvent B.In addition, enforcement test similarly to Example 1.
Embodiment 3
In the glass reactor of agitating wing and condenser is housed, CR (electrochemical industry DCR-10:MS (2+2.5) 100 ℃=30) is dissolved among the mixed organic solvents A of 150 parts of toluene and 250 parts of MEK for 100 parts.Then, add 60 parts of MMA, in air atmosphere, temperature is remained on 80 ℃.
The solid formation of calculating the preceding CR of graft copolymerization similarly to Example 1 is divided into 17.86%.
Then, add 0.6 part of BPO, when stirring, begin graft polymerization reaction as polymerization starter.The BHT that adds 2.0 parts after reacting 5 hours stops polymerization, obtains chloroprene-based graft reaction liquid.The transformation efficiency of the MMA of the chloroprene-based graft reaction liquid of gained is 46%, is divided into 22.8% Gu form.
In addition, with Kreuk Field rotary type viscometer, recording 25 ℃ of the chloroprene-based graft reaction liquid of gained, the viscosity of 12rpm is 15000mPas.
The viscosity of 20 ℃ 10% toluene solution of the CR of present embodiment is 240mPas.
In the chloroprene-based graft reaction liquid of gained, add as 200 parts of the hexanaphthenes of organic solvent B (diluting solvent), obtain the chloroprene based graft adhesive that evaporation rate slows down to some extent, and implement test similarly to Example 1.
Comparative example 1
In the glass reactor of agitating wing and condenser is housed, CR (electrochemical industry A-90:MS (2+2.5) 100 ℃=48) is dissolved in the mixed solvent of 400 parts of toluene and 200 parts of MEK for 100 parts.Then, add 60 parts of MMA, in air atmosphere, temperature is remained on 80 ℃.
The solid formation of calculating the preceding CR of graft copolymerization similarly to Example 1 is divided into 13.16%.
Then, add 0.55 part of BPO, when stirring, begin graft polymerization reaction as polymerization starter.The BHT that adds 2.0 parts after reacting 5 hours stops polymerization.The transformation efficiency of MMA is 44%, is divided into 16.7% Gu form.
In addition, with Kreuk Field rotary type viscometer, recording 25 ℃ of the gained polymeric solution, the viscosity of 12rpm is 4200mPas.
The viscosity of 20 ℃ 10% toluene solution of the CR of this comparative example is 550mPas.
Except gained graft reaction liquid is directly used as graft adhesive, carry out test similarly to Example 1.
Comparative example 2
In the glass reactor of agitating wing and condenser is housed, CR (electrochemical industry A-90 :) is dissolved in the mixed solvent of 150 parts of toluene, 250 parts of MEK and 200 parts of hexanaphthenes for 100 parts.Then, add 60 parts of MMA, in air atmosphere, temperature is remained on 70 ℃.
The solid formation of calculating the preceding CR of graft copolymerization similarly to Example 1 is divided into 13.16%.
Then, add 0.6 part of BPO, when stirring, begin graft polymerization reaction as polymerization starter.The BHT that adds 2.0 parts after reacting 5 hours stops polymerization.The transformation efficiency of MMA is 10%, is divided into 14.0% Gu form.
In addition, with Kreuk Field rotary type viscometer, recording 25 ℃ of the gained polymeric solution, the viscosity of 12rpm is 800mPas.
In addition, under the situation that polymerization time is extended to 8 hours, the adding rate of MMA is 22%, also 40～50% of miss the mark.
The viscosity of 20 ℃ 10% toluene solution of the CR of this comparative example is identical with comparative example 1, is 550mPas.
Except gained graft reaction liquid is directly used as graft adhesive, carry out test similarly to Example 1.
Test-results is summarized in table 1.From table 1 decidable, utilize method of the present invention can not cause detrimentally affect to bonding rerum natura, can regulate the evaporation rate of the organic solvent that is used for the sovprene based graft adhesive arbitrarily.
Table 1
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Comparative example 1 | Comparative example 2 | |
| Used polymkeric substance mooney viscosity 10% toluene solution viscosity [mpas] | ??A-30/A-70 ??20/40 ??250 | ??A-30/A-70 ??20/40 ??250 | ??DCR-10 ??30 ??240 | ??A-90 ??48 ??550 | ??A-90 ??48 ??550 |
| Polymerization formula [mass parts] CR MMA toluene MEK hexanaphthene polymerization starter BPO | ??100 ??60 ??150 ??250 ??- ??0.6 | ??100 ??60 ??150 ??250 ??- ??0.6 | ??100 ??60 ??150 ??250 ??- ??0.6 | ??100 ??60 ??400 ??200 ??- ??0.55 | ??100 ??60 ??150 ??250 ??200 ??0.6 |
| Solid formation branch [%] before the polymerization | ??17.86 | ??17.86 | ??17.86 | ??13.16 | ??13.16 |
| The polymerization result polymerization temperature [℃] the solid branch [%] that forms of viscosity (25 ℃) [mPas] MMA percent polymerization [%] | ??80 ??14500 ??45 ??22.8 | ??80 ??14500 ??45 ??22.8 | ??80 ??15000 ??46 ??22.8 | ??80 ??4200 ??44 ??16.7 | ??70 ??800 ??10 ??14.0 |
| Dilution organic solvent [mass parts] hexanaphthene dimethylbenzene octane | ??200 ??- ??- | ??- ??100 ??100 | ??200 ??- ??- | ??- ??- ??- | ??- ??- ??- |
| The solid formation of tackiness agent rerum natura viscosity (25 ℃) [mPas] divided [%] | ??1600 ??16.8 | ??1800 ??16.8 | ??1700 ??16.8 | ??4200 ??16.7 | ??800 ??14.0 |
| The 50% volatilization time of evaporation rate [minute] | ??26 | ??50 | ??26 | ??45 | ??30 |
| Bonding rerum natura normality intensity [N/mm] | ??1.4 | ??1.4 | ??1.5 | ??1.5 | ??0.4 |
The possibility of utilizing on the industry
Purposes to the chlorobutadiene based graft adhesive that makes by preparation method of the present invention is not particularly limited, can be used for each field, the bonded body that the polyvinyl chloride system of being specially adapted to or polyurethane synthetic leather processed, rubber, plastic material etc. are difficult bonding, the adhesive that can be used as in shoe industry and the case and bag manufacturing industry uses.
In addition, the graft adhesive of the present invention's acquisition also can be used as the silane coupling agent use. In this case, general solid composition amount ratio uses few as adhesive, so more important when the control ratio of the evaporation rate of solvent uses as adhesive, the present invention can effectively use.
Claims (7)
1. the preparation method of chloroprene based graft adhesive, it is characterized in that, when preparation makes sovprene and methyl methacrylate-grafted polymeric chloroprene based graft adhesive, be higher than 70 ℃ independent organic solvent A or contain in the mixed solvent of organic solvent orange 2 A in solubilized sovprene and boiling point or azeotropic point, after making sovprene and methyl methacrylate carry out graft polymerization, add another organic solvent B more separately or contain the mixed solvent of organic solvent B.
2. the preparation method of chloroprene based graft adhesive as claimed in claim 1, its feature also be, independent organic solvent A contain the boiling point of mixed solvent of organic solvent orange 2 A or azeotropic point more than 80 ℃.
3. the preparation method of chloroprene based graft adhesive as claimed in claim 1 or 2, its feature also is, the amount of the organic solvent A when being used for graft polymerization is 50～80 quality % of organic solvent total amount, and the amount of the organic solvent B that adds after graft polymerization is 50～20 quality %.
4. as the preparation method of each described chloroprene based graft adhesive in the claim 1～3, its feature is that also the solid formation of the sovprene before the graft copolymerization divides more than 15%.
5. as the preparation method of each described chloroprene based graft adhesive in the claim 1～4, its feature also is, 100 ℃ of mooney viscosity MS (2+2.5) that are used for the sovprene of graft polymerization are below 40 or the viscosity of 20 ℃ 10% toluene solution is below the 400mPas.
6. as the preparation method of each described chloroprene based graft adhesive in the claim 1～5, its feature is that also the organic solvent A of the solvent during as graft polymerization is the mixed solvent that contains toluene and ethyl methyl ketone.
7. chloroprene based graft adhesive, this tackiness agent makes by each described preparation method in the claim 1～6, it is characterized in that, and viscosity is 1000～5000mPas, is divided into 12～22% Gu form.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP295887/2003 | 2003-08-20 | ||
| JP2003295887A JP4195647B2 (en) | 2003-08-20 | 2003-08-20 | Method for producing chloroprene graft adhesive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1705727A true CN1705727A (en) | 2005-12-07 |
| CN100497511C CN100497511C (en) | 2009-06-10 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800013523A Expired - Fee Related CN100497511C (en) | 2003-08-20 | 2004-08-20 | Process for producing chloroprene-based graft adhesive |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP4195647B2 (en) |
| CN (1) | CN100497511C (en) |
| WO (1) | WO2005019368A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921563A (en) * | 2010-09-16 | 2010-12-22 | 武汉理工大学 | Adhesive for powder metallurgy-macromolecule self-lubricating composite and preparation method thereof |
| CN108084928A (en) * | 2017-11-16 | 2018-05-29 | 武汉国利精细科技有限公司 | A kind of sealing bags application specific architecture fluid sealant and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102746472B (en) * | 2012-04-20 | 2015-03-25 | 苏州兴业材料科技股份有限公司 | Special modified polypropylene resin and preparation method thereof |
| CN102863934A (en) * | 2012-08-28 | 2013-01-09 | 东莞市万钧化工新材料科技有限公司 | Method for preparing heat-resistant modified water-based chloroprene rubber adhesive and application |
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|---|---|---|---|---|
| JPS5834513B2 (en) * | 1974-03-22 | 1983-07-27 | 電気化学工業株式会社 | Adhesive base composition |
| JPS55139409A (en) * | 1979-04-16 | 1980-10-31 | Denki Kagaku Kogyo Kk | Graft copolymer composition |
| CN85105447B (en) * | 1985-07-11 | 1988-03-02 | 成都科技大学 | Simple method for preparation of graft copolymers |
| JPH01123882A (en) * | 1987-11-10 | 1989-05-16 | Tosoh Corp | Preparation of adhesive |
| JP2778096B2 (en) * | 1989-04-07 | 1998-07-23 | 東ソー株式会社 | Solid grafted chloroprene polymer for adhesives and method for producing the same |
| JP2767875B2 (en) * | 1989-04-28 | 1998-06-18 | 東ソー株式会社 | Adhesive manufacturing method |
| JP2567762B2 (en) * | 1991-09-28 | 1996-12-25 | アイカ工業株式会社 | adhesive |
| JP2691961B2 (en) * | 1993-03-05 | 1997-12-17 | ノガワケミカル株式会社 | Modified chloroprene synthetic rubber adhesive composition |
-
2003
- 2003-08-20 JP JP2003295887A patent/JP4195647B2/en not_active Expired - Fee Related
-
2004
- 2004-08-20 WO PCT/JP2004/012016 patent/WO2005019368A1/en active Application Filing
- 2004-08-20 CN CNB2004800013523A patent/CN100497511C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101921563A (en) * | 2010-09-16 | 2010-12-22 | 武汉理工大学 | Adhesive for powder metallurgy-macromolecule self-lubricating composite and preparation method thereof |
| CN101921563B (en) * | 2010-09-16 | 2012-11-07 | 武汉理工大学 | Adhesive for powder metallurgy-macromolecule self-lubricating composite and preparation method thereof |
| CN108084928A (en) * | 2017-11-16 | 2018-05-29 | 武汉国利精细科技有限公司 | A kind of sealing bags application specific architecture fluid sealant and preparation method thereof |
| CN108084928B (en) * | 2017-11-16 | 2019-12-13 | 武汉国利精细科技有限公司 | Special structural sealant for sealed packaging bag and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100497511C (en) | 2009-06-10 |
| JP4195647B2 (en) | 2008-12-10 |
| JP2005060624A (en) | 2005-03-10 |
| WO2005019368A1 (en) | 2005-03-03 |
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