CN106749920B - A kind of preparation method of organosilicon-modified styrene-acrylic graft starch glue - Google Patents
A kind of preparation method of organosilicon-modified styrene-acrylic graft starch glue Download PDFInfo
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- CN106749920B CN106749920B CN201611008177.1A CN201611008177A CN106749920B CN 106749920 B CN106749920 B CN 106749920B CN 201611008177 A CN201611008177 A CN 201611008177A CN 106749920 B CN106749920 B CN 106749920B
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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
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B31/00—Preparation of derivatives of starch
- C08B31/08—Ethers
- C08B31/12—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch
- C08B31/125—Ethers having alkyl or cycloalkyl radicals substituted by heteroatoms, e.g. hydroxyalkyl or carboxyalkyl starch having a substituent containing at least one nitrogen atom, e.g. cationic starch
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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
- C09J151/02—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 polysaccharides
Abstract
The invention discloses a kind of organosilicon-modified styrene-acrylic graft starch glue and preparation method thereof, using starch as primary raw material, obtain after microwave physical modification, cation-modified and organosilicon and phenylpropyl alcohol graft copolymerization.Organosilicon-modified styrene-acrylic graft starch glue of the invention and preparation method thereof has grafting rate height, the feature that adhesion strength is good, degradable and low in cost.
Description
Technical field
The present invention relates to amylan technical field, specially a kind of organosilicon-modified styrene-acrylic graft starch glue and its preparation side
Method.
Background technique
Starch is a kind of cheap renewable natural macromolecular material, its nontoxic, easily biological-degradable.It further develops and has
Effect has become the project of investigation of materials field common concern using starch resource.Its mobility when starch is directly as adhesive,
Permeability and mechanical property are poor.The spy that can change starch is modified to starch with the method for physics, chemistry or biology
Property, it is the effective ways for preparing starch adhesive.At present most starches adhesive be all by oxidation, be crosslinked, esterification etc. changes
Property method, although improving the performances such as mobility, permeability, with synthesis macromolecular adhesive adhesive strength compared with there are still
Biggish gap.By starch and olefin monomer graft copolymerization, the olefin monomer made is connect the present invention with certain degree of polymerization
On branch to starch molecular chain, to impart starch adhesive with new performance.Since the method can pass through the choosing of grafted monomers
Select, the design of grafting density and branch lengths and control regulate and control the performance of copolymer, to reach regulation starch adhesive
Performance is suitable with Polymer Synthesizing adhesive.Retain biodegradable performance again, the requirement with the mankind to sustainable development is mutually fitted
It answers, meets environmentally protective theory.
Summary of the invention
The object of the present invention is to provide a kind of organosilicon-modified styrene-acrylic graft starch glue and preparation method thereof, have grafting rate
Height, the feature that adhesion strength is good, degradable and low in cost.
The present invention can be achieved through the following technical solutions:
The invention discloses a kind of preparation methods of organosilicon-modified styrene-acrylic graft starch glue, comprising the following steps:
A, microwave physical modification
Add water to adjust moisture commercially available common starch to be 20-30%, be crushed, the tunnel for being then 60~120kw through overpower
Formula continuous multi-resonant chamber microwave radiation equipment in road is irradiated 15~45 minutes, is ground by connected superfine pulverizer, into dust-removal cloth-bag, is received
The starch partial size collected is 4~20 μm, and moisture is 2~5%.There is large specific surface area by the starch of microwave modification, reaction is lived
The high feature of property, the reaction efficiency of 20-35% can be improved in the subsequent graft copolymerization stage；
B, cation-modified
It will be put into blending tank by 100 parts by weight of microwave physically denatured starch, it is 30 that concentration is added in whipping process
20~30 parts by weight of~50% isopropanol water solution are added 1~3 parts by weight of sodium hydroxide powder after stirring 15~45min, stir
3~15 parts by weight of (the chloro- 2- hydroxypropyl of 3-) trimethyl ammonium chloride are added after mixing 20~60min, stir 20~60min.Pumping is expected
It is reacted in reactor tank, reaction temperature is 50~80 DEG C, and the reaction time is 60~180min；After completion of the reaction by it is cooling,
It neutralizes, is dehydrated, is dry, broken, obtain the cationic modified starch that degree of substitution is 0.02~0.08；
C, organosilicon and phenylpropyl alcohol graft copolymerization
By in cationic modified starch, deionized water, 0.005~0.05 parts by weight of medium temperature amylase investment reaction kettle, stir
Mix 10~30min.Heating device is opened, temperature controls at 70~80 DEG C, keeps the temperature 30~60min, make starch gelatinization abundant in this way,
Then gelatinized corn starch liquid temperature is controlled at 85~90 DEG C, is passed through nitrogen, styrene, acrylic acid, third is slowly added to after 5~20min
0.1~0.5 parts by weight of olefin(e) acid butyl ester, organosilicon and water-soluble azo initiator are added time control and add in 1~2h, keep the temperature
2~4h is reacted, it is cooling, it discharges, weighing, packaging is got product.
Preferably, in the organosilicon and phenylpropyl alcohol graft copolymerization, cationic starch: styrene: butyl acrylate: propylene
Acid: the quality proportioning of organosilicon is 1:0.1~0.5:0.1~0.5:0.1~0.3:0.05~0.2.
Preferably, the partial size of the commercially available common starch is 25~60 μm, and moisture is 9~17%.
Preferably, in the organosilicon and phenylpropyl alcohol graft copolymerization, cationic starch: styrene: butyl acrylate: propylene
Acid: the quality proportioning of organosilicon is 1:0.3:0.3:0.3:0.1.
Preferably, the organosilicon is γ-aminopropyl triethoxysilane and vinyltrimethoxysilane.
The resulting amylan of preparation method of more than one organosilicon-modified styrene-acrylic graft starch glue.
A kind of organosilicon-modified styrene-acrylic graft starch glue of the present invention and preparation method thereof, have it is following the utility model has the advantages that
The first, grafting rate is high, and the present invention uses microwave and connected superfine pulverizer pretreated starch, can be improved starch-grafted
Rate is laid a good foundation to improve adhesive bond strength in next step；
The second, adhesion strength is good, and organic-silicon-modified cationic starch grafting styrene-acrylic emulsion grafting rate of the invention is high, passes through
The addition that organosilicon modifier is added increases the adhesion strength and flexibility of adhesive；
Third, degradable, organic-silicon-modified cationic starch grafting styrene-acrylic emulsion of the present invention uses natural high
Molecule and graft copolymerization of vinyl monomer, the biodegradability that not only there is synthesis high molecular material not have, but also improve general
Logical modified starch slow drying speed and the low disadvantage of adhesion strength；
4th, low in cost, this product is at low cost compared with synthesis macromolecule adhesive on the market, performance phase
When.
Specific embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, below with reference to embodiment and to this
Invention product is described in further detail.
Embodiment 1
The invention discloses a kind of organosilicon-modified styrene-acrylic graft starch glue, through the following steps that prepare:
A, microwave physical modification
Add water to adjust moisture commercially available common starch to be 20-30%, be crushed, the tunnel type for being then 120kw through overpower
Continuous multi-resonant chamber microwave radiation equipment is irradiated 30 minutes, is ground by connected superfine pulverizer, into dust-removal cloth-bag, the shallow lake that is collected into
Powder diameter is 4~20 μm, and moisture is 2~5%；
B, cation-modified
It will be put into blending tank by 100 parts by weight of microwave physically denatured starch, it is 30 that concentration is added in whipping process
20 parts by weight of~50% isopropanol water solution are added 2 parts by weight of sodium hydroxide powder after stirring 45min, are added after stirring 20min
The chloro- 2- hydroxypropyl of 3-) 15 parts by weight of trimethyl ammonium chloride, stir 40min.Pumping, which is expected in reactor tank, is reacted, reaction temperature
It is 500 DEG C, reaction time 180min；Pass through cooling, neutralization after completion of the reaction, be dehydrated, be dry, broken, obtaining degree of substitution is
0.02~0.08 cationic modified starch；
C, organosilicon and phenylpropyl alcohol graft copolymerization
By in cationic modified starch, deionized water, 0.0275 parts by weight of medium temperature amylase investment reaction kettle, stir
10min.Heating device is opened, temperature controls at 80 DEG C, keeps the temperature 45min, make starch gelatinization abundant in this way, then by gelatinized corn starch liquid
Temperature is controlled at 85 DEG C, is passed through nitrogen, and styrene, acrylic acid, butyl acrylate, organosilicon and water-soluble are slowly added to after 20min
Property 0.3 parts by weight of azo initiator, time control is added to be added in 1h, insulation reaction 4h, cooling, is discharged, weighing is packed to obtain the final product
Finished product.
In the present embodiment, in the organosilicon and phenylpropyl alcohol graft copolymerization, cationic starch: styrene: acrylic acid fourth
Ester: acrylic acid: the quality proportioning of organosilicon is 1:0.3:0.1:0.3:0.025.The partial size of the commercially available common starch be 25~
60 μm, moisture is 9~17%.The organosilicon is γ-aminopropyl triethoxysilane and vinyltrimethoxysilane.
Embodiment 2
The invention discloses a kind of organosilicon-modified styrene-acrylic graft starch glue, through the following steps that prepare:
A, microwave physical modification
Add water to adjust moisture commercially available common starch to be 20-30%, be crushed, then connect through the tunnel type that overpower is 90kw
Continuous multi-resonant chamber microwave radiation equipment is irradiated 15 minutes, is ground by connected superfine pulverizer, into dust-removal cloth-bag, the starch that is collected into
Partial size is 4~20 μm, and moisture is 2~5%；
B, cation-modified
It will be put into blending tank by 100 parts by weight of microwave physically denatured starch, it is 30 that concentration is added in whipping process
30 parts by weight of~50% isopropanol water solution are added 1 parts by weight of sodium hydroxide powder after stirring 30min, are added after stirring 60min
The chloro- 2- hydroxypropyl of 3-) 9 parts by weight of trimethyl ammonium chloride, stir 20min.Pumping, which is expected in reactor tank, is reacted, and reaction temperature is
80 DEG C, reaction time 90min；Pass through cooling, neutralization after completion of the reaction, be dehydrated, be dry, broken, obtaining degree of substitution is 0.02
~0.08 cationic modified starch；
C, organosilicon and phenylpropyl alcohol graft copolymerization
By in cationic modified starch, deionized water, 0.005 parts by weight of medium temperature amylase investment reaction kettle, stir
30min.Heating device is opened, temperature controls at 75 DEG C, keeps the temperature 30min, make starch gelatinization abundant in this way, then by gelatinized corn starch liquid
Temperature is controlled at 90 DEG C, is passed through nitrogen, and styrene, acrylic acid, butyl acrylate, organosilicon and water-soluble are slowly added to after 13min
Property 0.1 parts by weight of azo initiator, time control is added to be added in 2h, insulation reaction 3h, cooling, is discharged, weighing is packed to obtain the final product
Finished product.
In the present embodiment, in the organosilicon and phenylpropyl alcohol graft copolymerization, cationic starch: styrene: acrylic acid fourth
Ester: acrylic acid: the quality proportioning of organosilicon is 1:0.3:0.1:0.3:0.12.The partial size of the commercially available common starch be 25~
60 μm, moisture is 9~17%.The organosilicon is γ-aminopropyl triethoxysilane and vinyltrimethoxysilane.
Embodiment 3
The invention discloses a kind of organosilicon-modified styrene-acrylic graft starch glue, through the following steps that prepare:
A, microwave physical modification
Add water to adjust moisture commercially available common starch to be 20-30%, be crushed, then connect through the tunnel type that overpower is 60kw
Continuous multi-resonant chamber microwave radiation equipment is irradiated 45 minutes, is ground by connected superfine pulverizer, into dust-removal cloth-bag, the starch that is collected into
Partial size is 4~20 μm, and moisture is 2~5%；
B, cation-modified
It will be put into blending tank by 100 parts by weight of microwave physically denatured starch, it is 30 that concentration is added in whipping process
25 parts by weight of~50% isopropanol water solution are added 3 parts by weight of sodium hydroxide powder after stirring 15min, are added after stirring 40min
3 parts by weight of (the chloro- 2- hydroxypropyl of 3-) trimethyl ammonium chloride stir 60min.Pumping, which is expected in reactor tank, is reacted, reaction temperature
It is 65 DEG C, reaction time 60min；Pass through cooling, neutralization after completion of the reaction, be dehydrated, be dry, broken, obtaining degree of substitution is
0.02~0.08 cationic modified starch；
C, organosilicon and phenylpropyl alcohol graft copolymerization
By in cationic modified starch, deionized water, 0.05 parts by weight of medium temperature amylase investment reaction kettle, 20min is stirred.
Heating device is opened, temperature controls at 70 DEG C, keeps the temperature 60min, make starch gelatinization abundant in this way, then by gelatinized corn starch liquid temperature control
System is passed through nitrogen, styrene, acrylic acid, butyl acrylate, organosilicon and water-soluble azo is slowly added to after 5min at 88 DEG C
0.3 parts by weight of initiator are added time control and add in 1h, and insulation reaction 4h is cooling, discharges, and weighing, packaging is got product.
In the present embodiment, in the organosilicon and phenylpropyl alcohol graft copolymerization, cationic starch: styrene: acrylic acid fourth
Ester: acrylic acid: the quality proportioning of organosilicon is 1:0.5:0.3:0.1:0.2.The partial size of the commercially available common starch is 25~60
μm, moisture is 9~17%.The organosilicon is γ-aminopropyl triethoxysilane and vinyltrimethoxysilane.
Embodiment 4
The invention discloses a kind of organosilicon-modified styrene-acrylic graft starch glue, through the following steps that prepare:
A, microwave physical modification
Add water to adjust moisture commercially available common starch to be 20-30%, be crushed, then connect through the tunnel type that overpower is 80kw
Continuous multi-resonant chamber microwave radiation equipment is irradiated 35 minutes, is ground by connected superfine pulverizer, into dust-removal cloth-bag, the starch that is collected into
Partial size is 4~20 μm, and moisture is 2~5%；
B, cation-modified
It will be put into blending tank by 100 parts by weight of microwave physically denatured starch, it is 30 that concentration is added in whipping process
1.3 parts by weight of sodium hydroxide powder are added after stirring 25min in 28 parts by weight of~50% isopropanol water solution, add after stirring 50min
Enter 6 parts by weight of (the chloro- 2- hydroxypropyl of 3-) trimethyl ammonium chloride, stirs 20~60min.Pumping, which is expected in reactor tank, is reacted, instead
Answering temperature is 60 DEG C, reaction time 100min；Pass through cooling, neutralization after completion of the reaction, be dehydrated, be dry, broken, is replaced
The cationic modified starch that degree is 0.02~0.08；
C, organosilicon and phenylpropyl alcohol graft copolymerization
By in cationic modified starch, deionized water, 0.035 parts by weight of medium temperature amylase investment reaction kettle, stir
13min.Heating device is opened, temperature controls at 78 DEG C, keeps the temperature 50min, make starch gelatinization abundant in this way, then by gelatinized corn starch liquid
Temperature is controlled at 87 DEG C, is passed through nitrogen, and styrene, acrylic acid, butyl acrylate, organosilicon and water-soluble are slowly added to after 10min
Property 0.1~0.5 parts by weight of azo initiator, time control is added to be added in 1.2h, insulation reaction 2.4h, cooling, is discharged, is claimed
Weight, packaging are got product.
In the present embodiment, in the organosilicon and phenylpropyl alcohol graft copolymerization, cationic starch: styrene: acrylic acid fourth
Ester: acrylic acid: the quality proportioning of organosilicon is 1:0.1:0.5:0.13:0.05.The partial size of the commercially available common starch be 25~
60 μm, moisture is 9~17%.The organosilicon is γ-aminopropyl triethoxysilane and vinyltrimethoxysilane.
Embodiment 5
The invention discloses a kind of organosilicon-modified styrene-acrylic graft starch glue, through the following steps that prepare:
A, microwave physical modification
Add water to adjust moisture commercially available common starch to be 20-30%, be crushed, then connect through the tunnel type that overpower is 80kw
Continuous multi-resonant chamber microwave radiation equipment is irradiated 35 minutes, is ground by connected superfine pulverizer, into dust-removal cloth-bag, the starch that is collected into
Partial size is 4~20 μm, and moisture is 2~5%；
B, cation-modified
It will be put into blending tank by 100 parts by weight of microwave physically denatured starch, it is 30 that concentration is added in whipping process
1.3 parts by weight of sodium hydroxide powder are added after stirring 25min in 28 parts by weight of~50% isopropanol water solution, add after stirring 50min
Enter 6 parts by weight of (the chloro- 2- hydroxypropyl of 3-) trimethyl ammonium chloride, stirs 20~60min.Pumping, which is expected in reactor tank, is reacted, instead
Answering temperature is 60 DEG C, reaction time 100min；Pass through cooling, neutralization after completion of the reaction, be dehydrated, be dry, broken, is replaced
The cationic modified starch that degree is 0.02~0.08；
C, organosilicon and phenylpropyl alcohol graft copolymerization
By in cationic modified starch, deionized water, 0.035 parts by weight of medium temperature amylase investment reaction kettle, stir
13min.Heating device is opened, temperature controls at 78 DEG C, keeps the temperature 50min, make starch gelatinization abundant in this way, then by gelatinized corn starch liquid
Temperature is controlled at 87 DEG C, is passed through nitrogen, and styrene, acrylic acid, butyl acrylate, organosilicon and water-soluble are slowly added to after 10min
Property 0.1~0.5 parts by weight of azo initiator, time control is added to be added in 1.2h, insulation reaction 2.4h, cooling, is discharged, is claimed
Weight, packaging are got product.
In the present embodiment, the partial size of the commercially available common starch is 25~60 μm, and moisture is 9~17%.Have described
In machine silicon and phenylpropyl alcohol graft copolymerization, cationic starch: styrene: butyl acrylate: acrylic acid: the quality proportioning of organosilicon is 1:
0.3:0.3:0.3:0.1.The organosilicon is γ-aminopropyl triethoxysilane and vinyltrimethoxysilane.
Embodiment 6~12
The difference of embodiment 6~12 and embodiment 5 is the degree of substitution of cationic starch, other preparation steps and embodiment
5 is identical.
In order to verify performance of the invention, bond strength test is carried out to the resulting amylan of embodiment 6~12 respectively, is surveyed
Test result is as shown in table 1:
1 embodiment of table, 6~12 bond strength test result
Embodiment 13~14
Embodiment 13~14 is that cationic starch is different with the proportion of organosilicon from the difference of embodiment 5, other proportions
It is constant.
In order to verify performance of the invention, respectively to embodiment 13~14, resulting amylan carries out grafting rate and bonding
Strength test, test result are as shown in table 2:
1 embodiment 5 of table, 13~14 grafting rates and bond strength test result
| Embodiment 5 | Embodiment 13 | Embodiment 14 | |
| The proportion of starch and organosilicon | 1:0.1 | 1:0.05 | 1:0.2 |
| Grafting rate (%) | 55.62 | 34.25 | 46.34 |
| Adhesive strength (N/m) | 2846 | 2352 | 2912 |
The foregoing is only a preferred embodiment of the present invention, is not intended to limit the present invention in any form；It is all
The those of ordinary skill of the industry can be described in by specification and described above and swimmingly implement the present invention；But it is all familiar
Professional and technical personnel without departing from the scope of the present invention, makes using disclosed above technology contents
A little variation, modification and evolution equivalent variations, be equivalent embodiment of the invention；Meanwhile all realities according to the present invention
The variation, modification and evolution etc. of matter technology any equivalent variations to the above embodiments, still fall within technology of the invention
Within the protection scope of scheme.
Claims (6)
1. a kind of preparation method of organosilicon-modified styrene-acrylic graft starch glue, it is characterised in that the following steps are included:
A, microwave physical modification
Add water to adjust moisture commercially available common starch to be 20-30%, be crushed, then connect through the tunnel type that overpower is 60~120kw
Continuous multi-resonant chamber microwave radiation equipment is irradiated 15~45 minutes, is ground by connected superfine pulverizer, into dust-removal cloth-bag, is collected into
Starch partial size is 4~20 μm, and moisture is 2~5%；
B, cation-modified
It will be put into blending tank by 100 parts by weight of microwave physically denatured starch, it is 30~50% that concentration is added in whipping process
20~30 parts by weight of isopropanol water solution, stir 15~45min after be added 1~3 parts by weight of sodium hydroxide powder, stirring 20~
3~15 parts by weight of (the chloro- 2- hydroxypropyl of 3-) trimethyl ammonium chloride are added after 60min, stir 20~60min, pumping expects reactor tank
In reacted, reaction temperature be 50~80 DEG C, the reaction time be 60~180min；Pass through cooling, neutralization after completion of the reaction, take off
Water, is crushed drying, obtains the cationic modified starch that degree of substitution is 0.02~0.08；
C, organosilicon and phenylpropyl alcohol graft copolymerization
By in cationic modified starch, deionized water, 0.005~0.05 parts by weight of medium temperature amylase investment reaction kettle, 10 are stirred
~30min.Heating device is opened, temperature controls at 70~80 DEG C, keeps the temperature 30~60min, make starch gelatinization abundant in this way, then
Gelatinized corn starch liquid temperature is controlled at 85~90 DEG C, nitrogen is passed through, styrene, acrylic acid, acrylic acid is slowly added to after 5~20min
0.1~0.5 parts by weight of butyl ester, organosilicon and water-soluble azo initiator are added time control and add in 1~2h, insulation reaction 2
~4h, it is cooling, it discharges, weighing, packaging is got product.
2. the preparation method of organosilicon-modified styrene-acrylic graft starch glue according to claim 1, it is characterised in that: described
In organosilicon and phenylpropyl alcohol graft copolymerization, cationic starch: styrene: butyl acrylate: acrylic acid: the quality proportioning of organosilicon is
1:0.1~0.5:0.1~0.5:0.1~0.3:0.05~0.2.
3. the preparation method of organosilicon-modified styrene-acrylic graft starch glue according to claim 1, it is characterised in that: the city
The partial size for selling common starch is 25~60 μm, and moisture is 9~17%.
4. the preparation method of organosilicon-modified styrene-acrylic graft starch glue according to claim 2 or 3, it is characterised in that:
In the organosilicon and phenylpropyl alcohol graft copolymerization, cationic starch: styrene: butyl acrylate: acrylic acid: the quality of organosilicon is matched
Than for 1:0.3:0.3:0.3:0.1.
5. the preparation method of organosilicon-modified styrene-acrylic graft starch glue according to claim 4, it is characterised in that: described to have
Machine silicon is γ-aminopropyl triethoxysilane and vinyltrimethoxysilane.
6. the preparation method of organosilicon-modified styrene-acrylic graft starch glue described in a kind of any one of Claims 1 to 5 claim
Resulting amylan.
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| CN110863375A (en) * | 2019-11-19 | 2020-03-06 | 湖州世合纺织有限公司 | Preparation method of low-salt efficient printing and dyeing paste for terylene |
| CN111876106B (en) * | 2020-08-12 | 2021-09-17 | 齐鲁工业大学 | Preparation method of binary organic silicon system modified starch-based wood adhesive, product and application thereof |
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| US4973680A (en) * | 1989-03-03 | 1990-11-27 | National Starch And Chemical Investment Holding Corporation | Organosiloxane-containing polysaccharides |
| CN102635019A (en) * | 2012-04-16 | 2012-08-15 | 陕西科技大学 | Preparation method of organic silicon surface sizing agent |
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|---|---|---|---|---|
| US4973680A (en) * | 1989-03-03 | 1990-11-27 | National Starch And Chemical Investment Holding Corporation | Organosiloxane-containing polysaccharides |
| CN102635019A (en) * | 2012-04-16 | 2012-08-15 | 陕西科技大学 | Preparation method of organic silicon surface sizing agent |
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