CN101285265A - Starch graft copolymer textile size and preparation method - Google Patents
Starch graft copolymer textile size and preparation method Download PDFInfo
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- CN101285265A CN101285265A CNA2008100507985A CN200810050798A CN101285265A CN 101285265 A CN101285265 A CN 101285265A CN A2008100507985 A CNA2008100507985 A CN A2008100507985A CN 200810050798 A CN200810050798 A CN 200810050798A CN 101285265 A CN101285265 A CN 101285265A
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- sizing agent
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Abstract
The invention relates to a starch graft polymer textile sizing agent and a method for producing the same. The textile sizing agent is a polymer of plant starch and an organic unsaturated monomer which are grafted and copolymerized. The weight average molecular weight Mw of the textile sizing agent is equal to 19228; the secondary transition point is 124.98 DEG C; the organic unsaturated monomer is acrylic acid, maleic anhydride or maleic resin or trans-butene diacid, alkyl methacrylate esters, maleic carbalkoxy or fumarate carbalkoxy; the plant starch and the organic unsaturated monomer are grafted and copolymerized in an organic chemical way to synthesize the starch graft polymer textile sizing agent. The textile sizing agent is biological and degradable chemically; therefore, the textile sizing agent can replace PVA to be the subject sizing agent in the slashing process, thereby greatly reducing the discharge of pollutant and contributing to the environmental protection.
Description
Technical field
The present invention relates to a kind of starch graft copolymer textile size and method for making, be specifically related to plant amylum and organic unsaturated monomer through vitochemical graft copolymerization and the synthetic spinning sizing agent that is used for the textile industry warp sizing.
Background technology
The main body slurry that textile industry is used for warp sizing is polyvinyl alcohol (PVA).Polyvinyl alcohol is difficult for degraded, fabric desizing exhaust emission environment.A lot of in the world developed countries refusal has the cloth import of PVA slurry.List of references: No. (2008) 15, " about carrying out the letter of " no PVA starching " popularization activity " capable association of middle cotton.
Summary of the invention
Be difficult for degraded, fabric desizing exhaust emission environment in order to solve polyvinyl alcohol.The invention provides a kind of starch graft copolymer textile size and method for making.
This spinning sizing agent is the polymer of plant amylum and organic unsaturated monomer graft copolymerization, and described organic unsaturated monomer is: acrylic acid; Cis-butenedioic anhydride or maleic acid or fumaric acid; Alkyl methacrylate; Maleic acid one alkane ester or fumaric acid one alkane ester.Its weight average molecular weight Mw=19228; Its second order transition point is: 124.98 ℃;
The method for making of a kind of starch graft copolymer textile size provided by the invention, its step and condition are as follows:
Reactant and percentage by weight proportioning are:
Plant amylum 27～33;
Acrylic acid 40～46;
Cis-butenedioic anhydride, maleic acid or fumaric acid 0.2～1;
Alkyl methacrylate 22～28;
Maleic acid one alkane ester or fumaric acid one alkane ester 6～8;
Initator is hydrogen peroxide-Liu acid Ya Tie -ascorbic acid system, and hydrogen peroxide:Liu acid Ya Tie : the weight ratio of ascorbic acid is:5:1:1, its consumption be reactant gross weight 0.8%～1.4%;
1) in the four-hole reactor of agitator, thermometer, condenser and nitrogen conduit is housed, the adding weight ratio is 10: 1 water and a cornstarch, stirs and feeds nitrogen down, and 90 ℃ of abundant gelatinizations were cooled to 50 ℃ and constant temperature after 30 minutes in constant temperature bath, and are standby;
2 take by weighing acrylic acid, cis-butenedioic anhydride, butyl methacrylate and monomethyl cis-butenedioic acid successively by proportioning drops in another reactor, and interior abundant mixing is standby;
Initator is dropped into above-mentioned steps 1) cornstarch fully stir evenly in the four-hole reactor of 50 ℃ of gelatinization and constant temperature, again with step 2) the fully monomer of mixing drop in the above-mentioned four-hole reactor, feeding under the nitrogen stirring, keep 45～55 ℃ and carried out graft copolymerization 5 hours, be neutralized to pH=6 with alkali (potassium or sodium or ammonia or amine), the discharging of cooling room temperature, drying, pulverizing obtain a kind of starch graft copolymer textile size.
The conventional using method of a kind of starch graft copolymer textile size: in the container of sizing mixing, add the water of institute's water requirement 70%, under agitation the investment subject slurry: a kind of starch graft copolymer textile size; Auxiliary slurry: converted starch; Auxiliary agent: preservative agent and lubricant; Be warming up to 90 ℃ under stirring, dissolved 20-50 minute, add residue 30% water, stir insulation down, be used for warp sizing.
Beneficial effect: this spinning sizing agent is biological, chemical degradable spinning sizing agent, replaces PVA fully as the main body slurry when warp sizing.Only in Zhong Guo the sewage discharge industry, textile printing and dyeing industry is one of great sewage discharge industry.Annual wastewater discharge surpasses 1,500,000,000 tons, and the PVA that is used in every year on the sizing fabric has more than 10 ten thousand tons, and the overwhelming majority is all discharged after printing and distribute the industry destarch through spinning, because PVA is difficult for degraded, and is difficult to reclaim, and brings very big difficulty to waste water control, and cost raises.A kind of starch graft copolymer textile size replaces PVA, replaces PVA fully as the main body slurry when warp sizing, can reduce the discharging of pollutant significantly, saves cost and is of value to environmental protection.
Description of drawings
Fig. 1 is a kind of starch graft copolymer textile size gel permeation chromatography figure GPC.
Fig. 2 is a kind of starch graft copolymer textile size differential scanning calorimetric spectrogram.
Fig. 3 is a kind of starch graft copolymer textile size infrared spectrogram.
The specific embodiment
Embodiment 1:
In the four-necked bottle that agitator, thermometer, condenser and nitrogen conduit are housed, add 300g water and cornstarch 30g, stir down and feed nitrogen, 90 ℃ of abundant gelatinizations were cooled to 50 ℃ and constant temperature after 30 minutes in constant temperature bath, and are standby.
Other gets a 500ml beaker, takes by weighing successively in acrylic acid 43g, cis-butenedioic anhydride 0.6g, butyl methacrylate 25g, the monomethyl cis-butenedioic acid 7g input beaker fully to mix, and is standby.
50 ℃ of of of of of of of gelatinization of Initator (hydrogen peroxide-Liu acid Ya Tie -ascorbic acid) 1.2g is dropped into above-mentioned cornstarch fully to be stirred evenly in the four-necked bottle of and constant temperature, again with in the 500ml beaker fully the monomer of mixing drop in the four-necked bottle, under feeding nitrogen stirs, 50 ℃ of of of of of of and carried of keep out graft copolymerization, 5 hours, (potassium or sodium or An Huo ) is neutralized to PH=6 with alkali, cooling discharging, drying, pulverizing obtain a kind of starch graft copolymer textile size. (brief note is BJZ-1)
Embodiment 2:
Cornstarch 27g, acrylic acid 46g, cis-butenedioic anhydride 0.2g, butyl methacrylate 22g, monomethyl cis-butenedioic acid 8g; 45 ℃ of reaction temperatures, initiator amount 1.4g, other technical process is identical with embodiment 1.Obtain a kind of starch graft copolymer textile size.(brief note is BJZ-2)
Embodiment 3:
Cornstarch 33g, acrylic acid 40g, cis-butenedioic anhydride 0.4g, butyl methacrylate 28g, monomethyl cis-butenedioic acid 6g; 55 ℃ of reaction temperatures.Initiator amount 0.9g, other technical process is identical with embodiment 1, obtains a kind of starch graft copolymer textile size.(brief note is BJZ-3).
The testing result of the embodiment of the invention 1,2,3 resulting a kind of starch graft copolymer textile sizes: weight average molecular weight Mw=19228.See accompanying drawing 1: a kind of starch graft copolymer textile size gel permeation chromatography figure GPC.
Second order transition point: 124.98 ℃; See accompanying drawing 2: a kind of starch graft copolymer textile size differential scanning calorimetric spectrogram.
Prove that through infrared spectrum analysis a kind of starch graft copolymer textile size has the graft copolymer of used monomer structure feature to exist.See accompanying drawing 3: a kind of starch graft copolymer textile size infrared spectrogram.
A kind of starch graft copolymer textile size BJZ-1 that the embodiment of the invention 1 provides and PVA slurry are as follows in JSSJ-83 sheet yarn starching test testing result:
Table one: formula of size (T/C45
S)
Annotate: MS-weaving oxidized starch auxiliary agent-weaving is (cured) auxiliary agent (two)-weaving preservative agent (sodium salicylate solution) with lubricator
Table two: slashing technique
Annotate: 45
sPolyester-cotton blend is from Long Tou Trading Co.
Table three: sizing physical index
Strength and elongation: space=the 500mm draw speed=test of 400mm/min filoplume: the YG172 type
Wear-resisting: speed=120mm/min weight=100g that pressurizes
In the table one of above-mentioned starching test testing result: No. 1 prescription is to be that main body is as the slurry comparative formula with PVA.No. 2 and No. 4 prescriptions are to be that main body is as comparative formula with BJZ-1.
In the data of above-mentioned starching test testing result table three: filoplume reduction rate (%) is better than for No. 4 No. 1; Enhancing power (%) is better than for No. 2 No. 1; Powerful (CN) is better than for No. 2 No. 1; Wear-resisting (inferior) is better than for No. 1 No. 2, No. 4; The rate of sizing (%) be higher than for No. 1 No. 2 1.81%, be higher than No. 4 1.32%, the high more within the specific limits effect to the slurry warp thread of warp sizing rate (%) is good more generally speaking." the general rate of sizing (%) is under the certain situation of slurry solid content if the rate of sizing (%) of No. 2 and No. 4 is brought up to No. 1 rate of sizing (%) level, can adjust within the specific limits by means such as Sizing machines pressure in the sizing process " then every test index data have raising.
A kind of starch graft copolymer textile size BJZ-2 that the embodiment of the invention 2 provides and PVA slurry are close with PVA slurry testing result with BJZ-1 in JSSJ-83 sheet yarn starching test testing result.
A kind of starch graft copolymer textile size BJZ-3 that the embodiment of the invention 3 provides and PVA slurry are tested testing result in the starching of JSSJ-83 sheet yarn: close with PVA slurry testing result with BJZ-1.
Claims (3)
1, a kind of starch graft copolymer textile size is characterized in that, this spinning sizing agent is the polymer of plant amylum and organic unsaturated monomer graft copolymerization, and described organic unsaturated monomer is: acrylic acid; Cis-butenedioic anhydride or maleic acid or fumaric acid; Alkyl methacrylate; Maleic acid one alkane ester or fumaric acid one alkane ester.
The composition of this spinning sizing agent and percentage by weight proportioning are:
Plant amylum is 27～33;
Acrylic acid 40～46;
Cis-butenedioic anhydride or maleic acid or fumaric acid 0.2～1;
Alkyl methacrylate 22～28;
Maleic acid one alkane ester or fumaric acid one alkane ester 6～8.
2, a kind of starch graft copolymer textile size as claimed in claim 1 is characterized in that, described starch graft copolymer textile size, its weight average molecular weight Mw=19228; Its second order transition point is: 124.98 ℃.
3, the method for making of a kind of starch graft copolymer textile size as claimed in claim 1 is characterized in that, its step and condition are as follows:
Reactant and percentage by weight proportioning are:
Plant amylum 27～33;
Acrylic acid 40～46;
Cis-butenedioic anhydride or maleic acid or fumaric acid 0.2～1;
Alkyl methacrylate 22～28;
Maleic acid one alkane ester or fumaric acid one alkane ester 6～8;
Initator is:hydrogen peroxide-Liu acid Ya Tie -ascorbic acid system, hydrogen peroxide:Liu acid Ya Tie : the weight ratio of ascorbic acid:5:1:1, its consumption be reactant gross weight 0.8%～1.4%;
1) in the four-hole reactor of agitator, thermometer, condenser and nitrogen conduit is housed, the adding weight ratio is 10: 1 water and a cornstarch, stirs and feeds nitrogen down, and 90 ℃ of abundant gelatinizations were cooled to 50 ℃ and constant temperature after 30 minutes in constant temperature bath, and are standby;
2) take by weighing acrylic acid, cis-butenedioic anhydride, butyl methacrylate and monomethyl cis-butenedioic acid successively by proportioning and drop in another reactor, fully mix, standby;
Initator is dropped into above-mentioned steps 1) cornstarch fully stir evenly in the four-hole reactor of 50 ℃ of gelatinization and constant temperature, again with step 2) the monomer of fully mixing drop in the above-mentioned four-hole reactor, feeding under the nitrogen stirring, keep 45～55 ℃ and carried out graft copolymerization 5 hours, be neutralized to pH=6 with potassium, sodium, ammonia or amine, the discharging of cooling room temperature, drying, pulverizing obtain a kind of starch graft copolymer textile size.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008100507985A CN101285265A (en) | 2008-06-05 | 2008-06-05 | Starch graft copolymer textile size and preparation method |
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| CNA2008100507985A CN101285265A (en) | 2008-06-05 | 2008-06-05 | Starch graft copolymer textile size and preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735392B (en) * | 2009-11-10 | 2011-07-20 | 天津工业大学 | Corn grafting starch and preparation method thereof |
| CN102926198A (en) * | 2012-10-26 | 2013-02-13 | 无锡裕通织造有限公司 | Spinning sizing agent |
| CN117384323A (en) * | 2023-12-12 | 2024-01-12 | 成都锂能科技有限公司 | Starch-based precursor material and preparation method and application thereof |
-
2008
- 2008-06-05 CN CNA2008100507985A patent/CN101285265A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101735392B (en) * | 2009-11-10 | 2011-07-20 | 天津工业大学 | Corn grafting starch and preparation method thereof |
| CN102926198A (en) * | 2012-10-26 | 2013-02-13 | 无锡裕通织造有限公司 | Spinning sizing agent |
| CN117384323A (en) * | 2023-12-12 | 2024-01-12 | 成都锂能科技有限公司 | Starch-based precursor material and preparation method and application thereof |
| CN117384323B (en) * | 2023-12-12 | 2024-03-08 | 成都锂能科技有限公司 | Starch-based precursor material and preparation method and application thereof |
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