CN107868303A - A kind of preparation method of modified collagen albumen rubber composite - Google Patents
A kind of preparation method of modified collagen albumen rubber composite Download PDFInfo
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- CN107868303A CN107868303A CN201711164013.2A CN201711164013A CN107868303A CN 107868303 A CN107868303 A CN 107868303A CN 201711164013 A CN201711164013 A CN 201711164013A CN 107868303 A CN107868303 A CN 107868303A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B15/00—Preparation of other cellulose derivatives or modified cellulose, e.g. complexes
- C08B15/02—Oxycellulose; Hydrocellulose; Cellulosehydrate, e.g. microcrystalline cellulose
-
- 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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- 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
- C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
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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
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Materials Engineering (AREA)
- Tires In General (AREA)
- Tyre Moulding (AREA)
Abstract
The invention discloses a kind of preparation method of modified collagen albumen rubber composite, first sodium metaperiodate, sodium hydrogensulfite are aoxidized and are grafted in the microcrystalline cellulose addition collagen solution of sulfonation modifying, add styrene and carry out solution polymerization, modified collagen protein material is obtained after spray drying, be well mixed with raw materials such as carbon black, rubber, by being kneaded, vulcanization prepare modified collagen albumen rubber composite.Rubber composite prepared by the present invention has the advantages of good mechanical property and water resistance are strong, quality is homogeneous, stable performance concurrently, and cost is cheap, green, has good environmental benefit and economic benefit.
Description
Technical field
The present invention relates to technical field of rubber material, more particularly to a kind of system of modified collagen albumen-rubber composite
Preparation Method.
Background technology
Carbon black is the most important reinforced filling of rubber industry due to having excellent strengthening action to rubber.But carbon black
Have the shortcomings that environmental pollution is serious, energy consumption is big, has reliability to oil as filler.Shortage and ring with fossil energy
The problems such as border is polluted becomes getting worse, and the continuous enhancing of people's environmental protection consciousness, utilizes natural renewable resource
The research that substitute as carbon black is used for elastomeric material increasingly attracts attention.
Collagen is a kind of natural macromolecular material, has unique filamentary structure and good biological degradability,
Fillibility is good, and raw material sources are extensive.Especially in the discarded object of leather industry, the content of protein more than 30%, and its
Middle collagen accounts for more than the 90% of albumen quality.It is that raw material refines collagen with the inferior cladding of process hides, tailing etc.,
And it is applied to reinforcing rubber, it can not only reduce environmental pollution, and there is good economic benefit.However, collagen egg
It is poor with the compatibility of elastomeric material in vain, easily reunite in rubber mass, and collagen water imbibition is strong, influences rubber
The water resistance of glue material so that collagen is restricted when as rubber reinforcing filler.
The content of the invention
The defects of the object of the invention is exactly to make up prior art, there is provided a kind of mass uniformity is good, water resistance is strong, property
The preparation method of modified collagen albumen-rubber composite that can be stable.
The present invention is achieved by the following technical solutions：
A kind of preparation method of modified collagen albumen-rubber composite, comprises the following steps：
（1）First 2-4 parts by weight microcrystalline cellulose is added in 20-40 parts by weight sodium periodate solutions and aoxidized in 30-50 DEG C of lucifuge
2-4h is reacted, 20-40 parts by weight solution of sodium bisulfite is added after obtained oxidation microcrystalline cellulose is washed with water in 60-
80 DEG C of sulfonation 2-4h, 80-100 parts by weight water is added after being washed with water again and is uniformly dispersed, adds 10-15 parts by weight collagens
2-4 parts by weight of styrene and 0.02-0.04 parts by weight potassium peroxydisulfate are added in nitrogen ceiling after stirring 1-2h in 85-90 DEG C
60-70 DEG C of reaction 3-5h under part, then spray drying obtain modified collagen protein material；
（2）By 1-2 parts by weight silane coupler KH-792,1-2 part by weight of zinc oxide, 2-4 parts by weight stearic acid, 0.5-1 weight
Part age resistor, 20-40 parts by weight of carbon black per, 20-40 parts by weight steps（1）Described modified collagen protein material and 80-100 weight
Part rubber mix is uniform, is first kneaded in two-roll mill, then adds 0.5-1 parts by weight accelerator, 1-2 parts by weight Sulfurs exist
150-160 DEG C of vulcanization, obtains modified collagen albumen-rubber composite on vulcanizing press；
The collagen is that leather discards collagen.
The mass concentration of the sodium periodate solution is 2-4g/L.
The mass concentration of the solution of sodium bisulfite is 10-15g/L.
The step（1）In spray drying EAT be 80-90 DEG C.
The rubber is one or several kinds of mixing in natural rubber, butadiene-styrene rubber, butadiene rubber.
It is an advantage of the invention that：
The present invention first adds the microcrystalline cellulose of sodium metaperiodate, sodium hydrogensulfite oxidation-sulfonation modifying in collagen solution
It is grafted, adds styrene and carry out solution polymerization, modified collagen protein material is obtained after spray drying, passes through sulfonation
The grafting of microcrystalline cellulose and collagen assigns modified collagen protein material good toughness, is assigned and changed by graft phenylethene
The property good water resistance of collagen material and the compatibility good with elastomeric material, the modified collagen protein material that will be obtained
Be well mixed with raw materials such as carbon black, rubber, by being kneaded, vulcanization prepare modified collagen albumen-rubber composite, so as to get
Rubber composite has the advantages of good mechanical property and water resistance are strong, quality is homogeneous, stable performance concurrently, and cost is low
It is honest and clean, green, there is good environmental benefit and economic benefit.
Embodiment
A kind of preparation method of modified collagen albumen-rubber composite, comprises the following steps：
（1）First 2 parts by weight microcrystalline celluloses are added in 30 DEG C of lucifuge oxidation reaction 2h in 20 parts by weight sodium periodate solutions, will
Obtained oxidation microcrystalline cellulose adds 20 parts by weight solution of sodium bisulfite in 60 DEG C of sulfonation 2h after being washed with water, use again
80 parts by weight water are added after water washing to be uniformly dispersed, and are added after 10 parts by weight collagens stir 1h in 85 DEG C and are added 2 weight
Part styrene and 0.02 parts by weight potassium peroxydisulfate 60 DEG C of reaction 3h under nitrogen protective condition, then spray drying obtain modified adhesive
Former protein material；
（2）By 1 parts by weight silane coupler KH-792,1 part by weight of zinc oxide, 2 parts by weight stearic acid, 0.5 parts by weight age resistor,
20 parts by weight of carbon black per, 20 parts by weight steps（1）Described modified collagen protein material and 80 parts by weight of rubber is well mixed, and is first existed
It is kneaded in two-roll mill, then adds the 150 DEG C of vulcanizations on vulcanizing press of 0.5 parts by weight accelerator, 1 parts by weight Sulfur,
Obtain modified collagen albumen-rubber composite；
The collagen is that leather discards collagen.
The mass concentration of the sodium periodate solution is 2g/L.
The mass concentration of the solution of sodium bisulfite is 10g/L.
The step（1）In spray drying EAT be 80 DEG C.
The rubber is butadiene-styrene rubber.
Claims (5)
1. a kind of preparation method of modified collagen albumen-rubber composite, it is characterised in that comprise the following steps：
（1）First 2-4 parts by weight microcrystalline cellulose is added in 20-40 parts by weight sodium periodate solutions and aoxidized in 30-50 DEG C of lucifuge
2-4h is reacted, 20-40 parts by weight solution of sodium bisulfite is added after obtained oxidation microcrystalline cellulose is washed with water in 60-
80 DEG C of sulfonation 2-4h, 80-100 parts by weight water is added after being washed with water again and is uniformly dispersed, adds 10-15 parts by weight collagens
2-4 parts by weight of styrene and 0.02-0.04 parts by weight potassium peroxydisulfate are added in nitrogen ceiling after stirring 1-2h in 85-90 DEG C
60-70 DEG C of reaction 3-5h under part, then spray drying obtain modified collagen protein material；
（2）By 1-2 parts by weight silane coupler KH-792,1-2 part by weight of zinc oxide, 2-4 parts by weight stearic acid, 0.5-1 weight
Part age resistor, 20-40 parts by weight of carbon black per, 20-40 parts by weight steps（1）Described modified collagen protein material and 80-100 weight
Part rubber mix is uniform, is first kneaded in two-roll mill, then adds 0.5-1 parts by weight accelerator, 1-2 parts by weight Sulfurs exist
150-160 DEG C of vulcanization, obtains modified collagen albumen-rubber composite on vulcanizing press；
A kind of preparation method of modified collagen albumen-rubber composite according to claim 1, it is characterised in that institute
State collagen and discard collagen for leather.
A kind of 2. preparation method of modified collagen albumen-rubber composite according to claim 1, it is characterised in that
The mass concentration of the sodium periodate solution is 2-4g/L.
A kind of 3. preparation method of modified collagen albumen-rubber composite according to claim 1, it is characterised in that
The mass concentration of the solution of sodium bisulfite is 10-15g/L.
A kind of 4. preparation method of modified collagen albumen-rubber composite according to claim 1, it is characterised in that
The step（1）In spray drying EAT be 80-90 DEG C.
A kind of 5. preparation method of modified collagen albumen-rubber composite according to claim 1, it is characterised in that
The rubber is one or several kinds of mixing in natural rubber, butadiene-styrene rubber, butadiene rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711164013.2A CN107868303A (en) | 2017-11-21 | 2017-11-21 | A kind of preparation method of modified collagen albumen rubber composite |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711164013.2A CN107868303A (en) | 2017-11-21 | 2017-11-21 | A kind of preparation method of modified collagen albumen rubber composite |
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| Publication Number | Publication Date |
|---|---|
| CN107868303A true CN107868303A (en) | 2018-04-03 |
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| CN201711164013.2A Pending CN107868303A (en) | 2017-11-21 | 2017-11-21 | A kind of preparation method of modified collagen albumen rubber composite |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100066005A (en) * | 2008-12-09 | 2010-06-17 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Rubber composition and elastomeric glove produced by using the same |
| CN102516617A (en) * | 2011-12-08 | 2012-06-27 | 无锡宝通带业股份有限公司 | High-strength laminated fire-retarding conveyer belt coating rubber, and preparation method thereof |
| CN105802232A (en) * | 2014-11-10 | 2016-07-27 | 吴杰 | Material for preparing artificial joint and preparation method thereof |
| WO2017007116A1 (en) * | 2015-07-03 | 2017-01-12 | 박현 | Eraser using natural starch composition and containing no plasticizers, and manufacturing method therefor |
-
2017
- 2017-11-21 CN CN201711164013.2A patent/CN107868303A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20100066005A (en) * | 2008-12-09 | 2010-06-17 | 쓰리엠 이노베이티브 프로퍼티즈 캄파니 | Rubber composition and elastomeric glove produced by using the same |
| CN102516617A (en) * | 2011-12-08 | 2012-06-27 | 无锡宝通带业股份有限公司 | High-strength laminated fire-retarding conveyer belt coating rubber, and preparation method thereof |
| CN105802232A (en) * | 2014-11-10 | 2016-07-27 | 吴杰 | Material for preparing artificial joint and preparation method thereof |
| WO2017007116A1 (en) * | 2015-07-03 | 2017-01-12 | 박현 | Eraser using natural starch composition and containing no plasticizers, and manufacturing method therefor |
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Application publication date: 20180403 |
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