CN104530837B - The preparation method of epoxidation solution polymerized butadiene styrene rubber coating - Google Patents
The preparation method of epoxidation solution polymerized butadiene styrene rubber coating Download PDFInfo
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- CN104530837B CN104530837B CN201410804726.0A CN201410804726A CN104530837B CN 104530837 B CN104530837 B CN 104530837B CN 201410804726 A CN201410804726 A CN 201410804726A CN 104530837 B CN104530837 B CN 104530837B
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- Prior art keywords
- butadiene styrene
- styrene rubber
- solution polymerized
- polymerized butadiene
- epoxidation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
Abstract
The preparation method of epoxidation solution polymerized butadiene styrene rubber coating, uses H2O2Cross acid system with HCOOH solution polymerized butadiene styrene rubber is carried out epoxidation modification to prepare epoxidation solution polymerized butadiene styrene rubber, the epoxidation solution polymerized butadiene styrene rubber of synthesis is dissolved in a certain amount of solvent, it is equipped with color stuffing, age resistor etc. are placed in grinding distribution in sand mill, treat that fineness reaches 20 μm dischargings and can obtain epoxidation solution polymerized butadiene styrene rubber coating component A, polyamide is dissolved in a certain amount of solvent, add firming agent and curing accelerator, it is placed in grinding distribution in sand mill, treat that fineness reaches 20 μm dischargings and can obtain epoxidation solution polymerized butadiene styrene rubber coating B component, by epoxidation solution polymerized butadiene styrene rubber coating A, B component mixes by a certain percentage, stir, after ripening, coated plate solidification can detect coating property.
Description
Technical field
The present invention relates to the preparation method of a kind of epoxidation solution polymerized butadiene styrene rubber coating, belong to polymer chemistry and polymer
Coating and combinations thereof thing technical field.
Background technology
Solution polymerized butadiene styrene rubber (SSBR) good combination property, serviceability are superior, introduce epoxide group, Ke Yizeng in SSBR
Adding SSBR polarity of chain, strengthen the interaction force between filler, raising SSBR rubber matrix is compatible with reinforcing agent
Property, the introducing of epoxide group simultaneously, drastically increase the solution polymerized butadiene styrene rubber adhesive force to base material.Epoxide group has stronger
Reactivity, provide conveniently for the further modification of SSBR, it is possible to provide solution polymerized butadiene styrene rubber coating normal temperature cure reaction spy
Property.Solution polymerized butadiene styrene rubber process for epoxidation mainly has: crossing acid system, peroxide method and ketone peroxide method, these methods are respectively arranged with
Its pluses and minuses.With H2O2With the acid system of crossing that HCOOH is representative, reaction condition gentleness, by-product is water, and environmental pollution is little, is epoxy
One of prefered method changed.
Invention CN201410508989 discloses a kind of high adhesion force stamping enamel, and its raw material includes by weight: third
Olefin(e) acid resin 80-83 part, ABS resin 23-26 part, ketone resin KR-12015-18 part, lignin fibre 4-5 part, sodium stearate
3.2-3.6 part, sodium hexameta phosphate 6.5-7 part, titanate coupling agent 1.8-2.1 part, nano titanium oxide 9-12 part, organic swelling
Soil 4-5 part, Nano sepiolite powder 14-17 part, Pulvis Talci 25-28 part, diphenyl phosphoester 6-9 part, polyphosphoric acid amine 12-15 part,
Nano-sized magnesium hydroxide 28-31 part, toughener 5.2-5.6 part, firming agent 1.2-1.5 part, defoamer 1.5-1.8 part, advection agent
1.6-1.9 part, antifungus agent 1-1.3 part, pigment 2.2-2.5 part, solvent 65-70 part.
The present invention prepares epoxidation solution polymerized butadiene styrene rubber coating because introducing epoxy radicals on solution polymerized butylbenzene strand, it is possible to resolve
The problem that the coating system that epoxy resin and rubber compatibility difference cause is unstable, reduces a large amount of coupling agent consumption to material
The impact of energy, base material not only can be played protection beautifying and decorating effect by epoxidation solution polymerized butadiene styrene rubber coating, and rubber is peculiar simultaneously
High resiliency can ensure that protection matrix has certain buffering in collision process, reduce the percussion to matrix.
Summary of the invention
Present invention aim at preparing a kind of epoxidation solution polymerized butadiene styrene rubber coating, use H2O2Acid system pair is crossed with HCOOH
Solution polymerized butadiene styrene rubber carries out epoxidation modification and prepares epoxidation solution polymerized butadiene styrene rubber, is dissolved in by the epoxidation butadiene-styrene rubber of synthesis and joining
In the solvent of side's amount, it is equipped with color stuffing, age resistor etc. and is placed in grinding distribution in sand mill, treat that fineness reaches 20 μm dischargings and can obtain epoxy
Change solution polymerized butadiene styrene rubber coating component A, polyamide is dissolved in the solvent of formula ratio, add firming agent and solidification promotes
Agent, is placed in grinding distribution in sand mill, treats that fineness reaches 20 μm dischargings and can obtain epoxidation solution polymerized butadiene styrene rubber coating B component, by ring
Oxidation solution polymerized butadiene styrene rubber coating A, B component mix by a certain percentage, stir, after ripening coated plate solidification can detect coating
Performance.
The preparation of epoxidation solution polymerized butadiene styrene rubber, syntheti c route is as follows:
(a)
(b)
The present invention can be achieved by the following measures:
In the container with agitator, reflux condenser, thermometer and constant pressure funnel, add the SSBR of formula ratio
With organic solvent (Pentamethylene. or toluene), stir under room temperature, treat that SSBR is completely dissolved post-heating to reaction temperature, addition formula ratio
Formic acid, drip the hydrogen peroxide of formula ratio by the speed of 1ml/min, control reaction temperature, after question response terminates, with distillation
Epoxidation solution polymerized butadiene styrene rubber (ESSBR) is washed till neutrality by water, when Pentamethylene. is solvent, boils off Pentamethylene. at 70 DEG C；Toluene is
During solvent, it is settled out under ESSBR, room temperature to be placed in vacuum drying oven with ethanol and is dried to constant weight.Epoxidation butylbenzene by synthesis
Rubber is dissolved in the solvent of formula ratio, is equipped with color stuffing, age resistor etc. and is placed in grinding distribution in sand mill, treats that fineness reaches 20 μm and goes out
Material can obtain epoxidation solution polymerized butadiene styrene rubber coating component A, is dissolved in the solvent of formula ratio by polyamide, add firming agent and
Curing accelerator, is placed in grinding distribution in sand mill, treats that fineness reaches 20 μm dischargings and can obtain epoxidation solution polymerized butadiene styrene rubber coating B group
Point, epoxidation solution polymerized butadiene styrene rubber coating A, B component are mixed by a certain percentage, stirs, coated plate solidifies after ripening
Detection coating property.
Wherein the consumption of synthesizing epoxy solution polymerized butadiene styrene rubber solvent for use Pentamethylene. or toluene is solution polymerized butadiene styrene rubber matter
6 ~ 12 times of amount, polyamide used is polyamide 6 50；The consumption of formic acid is the 0.5 ~ 1.5 of the amount of the material of carbon-carbon double bond
Times；The consumption of hydrogen peroxide is 0.5 ~ 1.5 times of the amount of the material of carbon-carbon double bond；Reaction temperature is 40 ~ 70 DEG C, and the response time is controlled
System is at 2 ~ 5h.In dope preparing process, solvent for use is Ketohexamethylene, and its consumption is respectively epoxidation solution polymerized butadiene styrene rubber and gathers
1 ~ 2 times of amide resin quality；Pigment used is Rutile type titanium dioxide, and its consumption is epoxidation solution polymerized butadiene styrene rubber quality
1/20~1/15；Filler is precipitated calcium carbonate, Pulvis Talci, organobentonite, and its total consumption is epoxidation solution polymerized butadiene styrene rubber matter
The 1/10 ~ 1/5 of amount；And precipitated calcium carbonate, Pulvis Talci, organobentonite consumption mass ratio are 2 ~ 3:3 ~ 2:1；Age resistor used
For 2 mercapto benzimidazole or 2,2,4-trimethyl-1,2-dihyaroquinoline polymer, its consumption is epoxidation solution polymerized butylbenzene
The 1/100 of rubber；Firming agent used and curing accelerator are respectively tetramethylthiuram disulfide, 2-benzothiazolyl mercaptan,
Its consumption is respectively the 1/100 and 5/1000 of polyamide；Epoxidation solution polymerized butadiene styrene rubber coating A, B component in mass ratio 8 ~
10:1 mixes.
Detailed description of the invention
The following is embodiments of the invention, but the present invention is not limited in the following example.
Embodiment 1
6.034gSSBR and 85.0ml toluene is added in agitator, reflux condenser, thermometer and constant pressure addition
In the container of the 500ml of funnel, stir under room temperature, treat that SSBR is completely dissolved post-heating to 50 DEG C, add 3.21ml formic acid, press
The speed of 1ml/min drips 7.64ml hydrogen peroxide, reacts 2 hours, with distilled water, ESSBR is washed till neutrality at 50 DEG C, uses
Ethanol is settled out under ESSBR, room temperature to be placed in vacuum drying oven and is dried to constant weight, and recording epoxy content after drying is 32.68%.
Embodiment 2
120.0gSSBR and 1440ml Pentamethylene. is added in and drips with agitator, reflux condenser, thermometer and constant voltage
In the container of the 2000ml of liquid funnel, stir under room temperature, treat that SSBR is completely dissolved post-heating to 40 DEG C, add 63.8ml formic acid,
Drip 76.0ml hydrogen peroxide by the speed of 3ml/min, react 2 hours at 40 DEG C, with distilled water, ESSBR is washed till neutrality,
Boiling off at 70 DEG C to be placed in vacuum drying oven under Pentamethylene., room temperature and be dried to constant weight, recording epoxy content after drying is 14.73%.
Embodiment 3
100g epoxidation butadiene-styrene rubber is dissolved in 150g Ketohexamethylene, adds 6g Rutile type titanium dioxide, 6g lightweight carbonic acid
Calcium, 6g Pulvis Talci, 3g organobentonite, 1g2-mercaptobenzimidazole etc. is placed in grinding distribution in sand mill, treats that fineness reaches 20 μ
M discharging can obtain epoxidation solution polymerized butadiene styrene rubber coating component A.
50g polyamide 6 50 resin is dissolved in 100g Ketohexamethylene, adds 0.5g tetramethylthiuram disulfide, 0.25g2-
Benzothiazolyl mercaptan, is placed in grinding distribution in sand mill, treats that fineness reaches 20 μm dischargings and can obtain the painting of epoxidation solution polymerized butadiene styrene rubber
Material B component.Epoxidation solution polymerized butadiene styrene rubber coating A, B component 8:1 in mass ratio are mixed, stirs, coated plate is solid after ripening
Change can detect coating property.
Claims (1)
1. the preparation method of epoxidation solution polymerized butadiene styrene rubber coating, it is characterised in that concrete preparation process is as follows:
(1) preparation of epoxidation solution polymerized butadiene styrene rubber:
In the container equipped with agitator, reflux condenser, thermometer and constant pressure funnel, add the solution polymerized butylbenzene of formula ratio
Rubber, Pentamethylene. or toluene, stir under room temperature, treats that solution polymerized butadiene styrene rubber is completely dissolved post-heating to reaction temperature, addition formula
The formic acid of amount, is dripped the hydrogen peroxide of formula ratio, controls certain reaction temperature by the speed of 1ml/min, after question response terminates,
With distilled water, epoxidation solution polymerized butadiene styrene rubber is washed till neutrality, when Pentamethylene. is solvent, at 70 DEG C, boils off Pentamethylene.；Toluene is molten
During agent, it is settled out under epoxidation solution polymerized butadiene styrene rubber, room temperature to be placed in vacuum drying oven with ethanol and is dried to constant weight, the most available
Epoxidation solution polymerized butadiene styrene rubber；
According to the preparation method of above-mentioned epoxidation solution polymerized butadiene styrene rubber, it is characterized by the consumption of solvent for use Pentamethylene. or toluene
For solution polymerized butadiene styrene rubber quality 6 ~ 12 times；The consumption of formic acid is 0.5 ~ 1.5 times of the amount of the material of carbon-carbon double bond；Hydrogen peroxide
0.5 ~ 1.5 times of amount of the material that consumption is carbon-carbon double bond；Reaction temperature is 70 DEG C；Response time controls at 2 ~ 5h；
(2) preparation of epoxidation solution polymerized butadiene styrene rubber coating:
The epoxidation solution polymerized butadiene styrene rubber of synthesis is dissolved in the solvent of formula ratio, is equipped with color stuffing, age resistor is placed in sand mill
Middle grinding distribution, treats that fineness reaches 20 μm dischargings and can obtain epoxidation solution polymerized butadiene styrene rubber coating component A, is dissolved in by polyamide and joining
In the solvent of side's amount, add firming agent and curing accelerator, be placed in grinding distribution in sand mill, treat that fineness reaches 20 μm dischargings and can obtain
Epoxidation solution polymerized butadiene styrene rubber coating B component, is mixed epoxidation solution polymerized butadiene styrene rubber coating A, B component in the ratio of formula ratio
Close, stir, after ripening coated plate solidification can detect coating property；
According to the preparation method of above-mentioned epoxidation solution polymerized butadiene styrene rubber coating, it is characterized by that polyamide used is polyamide
650；Solvent for use is Ketohexamethylene, and its consumption is respectively 1 ~ 2 times of epoxidation solution polymerized butadiene styrene rubber and polyamide quality；Institute
Being Rutile type titanium dioxide with pigment, its consumption is the 1/20 ~ 1/15 of epoxidation solution polymerized butadiene styrene rubber quality；Filler is lightweight carbon
Acid calcium, Pulvis Talci, organobentonite, its total consumption is the 1/10 ~ 1/5 of epoxidation solution polymerized butadiene styrene rubber quality；And lightweight carbon
Acid calcium, Pulvis Talci, organobentonite consumption mass ratio are 2 ~ 3:3 ~ 2:1；Age resistor used is 2 mercapto benzimidazole or 2,
2,4-trimethyl-1,2-dihyaroquinoline polymer, its consumption is the 1/100 of epoxidation solution polymerized butadiene styrene rubber；Firming agent used
Being respectively tetramethylthiuram disulfide, 2-benzothiazolyl mercaptan with curing accelerator, its consumption is respectively polyamide
1/100 and 5/1000；Epoxidation solution polymerized butadiene styrene rubber coating A, B component 8 ~ 10:1 in mass ratio mix.
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| CN201410804726.0A CN104530837B (en) | 2014-12-23 | 2014-12-23 | The preparation method of epoxidation solution polymerized butadiene styrene rubber coating |
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| CN104530837B true CN104530837B (en) | 2016-09-14 |
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| CN1113902C (en) * | 2000-10-26 | 2003-07-09 | 上海交通大学 | Process for preparing epoxidized elastomer |
| JP2007169558A (en) * | 2005-12-26 | 2007-07-05 | Sumitomo Rubber Ind Ltd | Rubber composition and pneumatic tire using the same |
| WO2013014999A1 (en) * | 2011-07-22 | 2013-01-31 | 住友ゴム工業株式会社 | Rubber composition for tread, and pneumatic tire |
| CN103788432B (en) * | 2012-11-01 | 2015-09-16 | 中国石油化工股份有限公司 | The application of rubber combination and vulcanized rubber and preparation method thereof and vulcanized rubber |
| CN103804602A (en) * | 2012-11-07 | 2014-05-21 | 中国石油化工股份有限公司 | Solution polymerized butadiene-styrene random copolymer, preparation method thereof, and applications of composite conditioning agent |
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Granted publication date: 20160914 Termination date: 20181223 |