CN105199038A - Water-soluble softness modifier for ramie fibers, and low temperature preparation method and application thereof - Google Patents
Water-soluble softness modifier for ramie fibers, and low temperature preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a water-soluble softness modifier for ramie fibers, and a low temperature preparation method and an application thereof, and belongs to the technical field of textile chemistry. The water-soluble softness modifier is prepared from 0.4-1wt% of an initiator, 5-15wt% of monomers, and the balance of water, wherein the initiator comprises hydrogen peroxide and vitamin C, and the monomers are acrylic acid and sodium methylacrylsulfonate. The water-soluble softness modifier for ramie fibers is prepared through the following steps: copolymerizing the acrylic acid and sodium methylacrylsulfonate monomers under 5-20DEG C low temperature conditions with water as a solvent and hydrogen peroxide and vitamin C as the initiator, and neutralizing by using an alkali solution. The softness modifier prepared in the invention is used to modify the ramie fibers, the bending strength of the modified ramie fibers is reduced by 15-20%, the tensile strength of the modified ramie fibers is increased by 8-11%, the initial elastic modulus of the modified ramie fibers is reduced by 16-21%, and the reduction of the initial elastic modulus shows enhancement of the softness of the ramie fibers.
Description
Technical field
The invention belongs to technical field of textile chemistry, be specifically related to a kind of water-soluble supple modifier for ramee and low temperature preparation method thereof and application.
Background technology
Textile industry is the conventional column industry of Chinese national economy and important people's livelihood industry, and be also the obvious industry of international competitive advantage, ramee is one of main raw material of weaving face fabric, in weaving face fabric, occupy critical role.China is one of country that hemp resource is the abundantest in the world, mainly contains ramie, sisal hemp, flax and yellow mestha etc., and the advantage such as wherein, ramie is high with its fast growth, output, easy survival is extensively planted in China.The fabric that ramee is made into has the advantages such as ventilative, moisture absorbing and sweat releasing, is desirable high-grade clothing fabric in summer.But due to the degree of crystallinity of ramee and orientation degree high, straight without the characteristic such as curling, cause that its flexibility is poor, spinning property is poor and have prodding and itching feeling to skin, the existence of these problems makes its advantage not bring into play fully, thus significantly limit its use.Cause the major cause of this phenomenon be due to the degree of crystallinity of ramee and orientation degree higher.If can partly eliminate ramee crystallizing field or at crystallizing field surface adsorption lubricant to change the structure of crystallizing field, so ramee is expanded by appropriateness, then flexibility will strengthen.
At present, more report is had for the flexibility arrangement of crudefiber crop both at home and abroad.Pan Hongwei, Zhang Hua, Liu Yanyan, Zhai Xuejun, Zhang Lichuan, Zhao Lei, Hu Xiudong, Wang Chengguo etc. have carried out flexibility modification to ramee respectively.From the result of these reports to fibre modification, although achieve some achievements, because bast-fibre reactive behavior is low, bring certain difficulty to flexibility modification, there is a lot of not enough going out in the modification of flexibility, at least the industrialization modification of bast-fibre flexibility not yet realizes.The flexibility research of crudefiber crop is the important topic that textile industry faces, and due to the constructional feature that crudefiber crop itself has, determines its flexibility not as good as cotton.Ramie has relatively many advantages in various crudefiber crop, and as growth cycle is short, easily survive, output is large, and therefore, improving its flexibility is current problem urgently to be resolved hurrily.
Commercially, the flexibility properties-correcting agent of fiber is more, mainly contains amido silicon oil system, fatty amide system etc.These softening agents due to wetting ability poor, make troubles to the Final finishing work of ramie fabric, particularly dye.Such as, application number be 201110210355.X application discloses a kind of Ambary modifier, cellulase 15 ~ 25 weight part, amido silicone oil microemulsion 10 ~ 20 weight part, sodium lauryl sulphate 1 ~ 10 weight part, sodium bicarbonate 1 ~ 5 weight part, this patent employs amido silicon oil, it makes linen have durable soft effect and good wetting ability and rebound resilience, but it is poor to the treatment effect of flaxen fiber, after flaxen fiber process, the spinning performance of flaxen fiber obviously reduces.In addition, Authorization Notice No. is the soft modification processing method that patent discloses a kind of ramee and fabric thereof of CN1253613C, by ramie after routine is come unstuck or ramie fabric floods in crosslinking Treatment liquid, dry, then under 120 ~ 140 DEG C of conditions, be cross-linked 3 ~ 8 minutes, wherein crosslinking Treatment liquid is made up of linking agent, swelling agent, wetting agent, catalyzer and water.But the method need at high temperature be carried out cross-linking modified, energy consumption is high, the method also utilizes multiple auxiliary agent as crosslinking Treatment liquid, but the mechanism of action of each auxiliary agent in soft modification processing method is not set forth clear, and these auxiliary agents are finally all cross-linked on ramee, and its unnecessary auxiliary agent not being removed process, these are attached to auxiliary agent on ramee and have a negative impact to the processing in ramee later stage and arrangement.
Summary of the invention
The present invention is directed to the deficiency of problem pointed in background technology and prior art existence, first object of the present invention is to provide a kind of water-soluble supple modifier for ramee, in addition, present invention also offers a kind of low temperature preparation method and application of the water-soluble supple modifier for ramee described above.
In order to realize above-mentioned first object of the present invention, contriver is through a large amount of experimental studies, have developed a kind of water-soluble supple modifier for ramee, described water-soluble supple modifier is prepared from by each raw material of following weight percent content: initiator 0.4 ~ 1%, monomer 5 ~ 15%, surplus is water, wherein, described initiator is hydrogen peroxide and vitamins C, and described monomer is vinylformic acid and methylpropene sodium sulfonate.
Further, methylpropene sodium sulfonate described in technique scheme and acrylic acid mol ratio are 1:1 ~ 4.
Further, hydrogen peroxide described in technique scheme and ascorbic mol ratio are 1:1 ~ 2.
Further, described in technique scheme, water is preferably pure water.
Another object of the present invention is to the low temperature preparation method providing a kind of water-soluble supple modifier for ramee described above, described method comprises the steps:
(1) take each component raw material, in there-necked flask, add water, then vinylformic acid and methylpropene sodium sulfonate are added in there-necked flask respectively, slowly stir, mix, and make the temperature of solution in flask maintain 5 ~ 20 DEG C;
(2) under the condition stirred, be added drop-wise in step (1) described flask respectively by hydrogen peroxide and the vitamins C aqueous solution, controlling time for adding is 2 ~ 3 hours, after dropwising simultaneously, continue stirring 2 ~ 3 hours, copolyreaction obtains vinylformic acid-methylpropene sodium sulfonate multipolymer;
(3) described for step (2) obtained vinylformic acid-methylpropene sodium sulfonate multipolymer alkali lye is neutralized to pH=7 ~ 8, i.e. the obtained described water-soluble supple modifier for ramee.
Further, methylpropene sodium sulfonate described in technique scheme and acrylic acid mol ratio are 1:1 ~ 4.
Further, hydrogen peroxide described in technique scheme and ascorbic mol ratio are 1:1 ~ 2.
Further, the sodium hydroxide solution of to be concentration the be 30wt% of alkali lye described in technique scheme.
Further, described in technique scheme, water is preferably pure water.
An also object of the present invention is the application providing a kind of above-mentioned obtained water-soluble supple modifier, that is, by obtained water-soluble supple modifier described above for the preparation of modified ramie, described modified ramie adopts following preparation method to obtain:
(1) ramee is immersed in the alkali lye of pH=11 ~ 12, be heated to 60 DEG C, flood 2 hours, in alkali lye, then add the above-mentioned obtained water-soluble supple modifier of the present invention, after slowly stirring, ramee is continued dipping 2h;
(2) after having flooded, ramee is taken out, is washed with water to fiber surface without any residual properties-correcting agent, then by the ramee vacuum-drying after washing, obtain the ramee that described flexibility is modified.
Further, described in technique scheme, the consumption of water-soluble supple modifier accounts for 1 ~ 8% of ramee weight.
Further, the sodium hydroxide solution of step (2) described alkali lye to be concentration be 30wt% in technique scheme.
Further, in technique scheme during ramee dipping, stir once at interval of 30min.
Full dissolubility supple modifier the present invention obtained carries out modification to ramee, and the hydroxide radical of ramee crystallizing field and the carboxylate radical generation esterification of properties-correcting agent, cause fibre crystallinity to decline, and the crystallizing field of fiber is reduced; In addition, the sulfonate group of softening agent is attached to fiber surface, sulfonate group is electronegative, weaken the frictional force between fiber, promote that fiber is more soft, therefore, properties-correcting agent prepared by the inventive method is obviously different from the soft mechanism of modification reported in the past to the soft mechanism of modification of ramee, is a kind of brand-new mechanism of modification.In addition, the polymerization of traditional Acrylic Acid Monomer generally adopts thermal degradation initiator, produces free radical, causes polyreaction to occur; The present invention adopts redox reaction to produce free radical at a lower temperature, in this reaction, hydrogen peroxide mainly plays the effect of oxygenant, vitamins C mainly plays the effect of reductive agent, at low temperatures, hydrogen peroxide and vitamins C generation redox reaction, produce free radical, cause vinylformic acid and methylpropene sodium sulfonate polymerization reaction take place.
Compared with prior art, the present invention has following beneficial effect:
(1) raw material sources of the present invention are extensive, and cost is low, and obtained supple modifier has stronger wetting ability, almost can dissolve each other with water, and the wastewater treatment modified to ramee is simple, to environment without any pollution, and environmental protection;
(2) supple modifier the present invention obtained carries out modification to ramee, modified, its flexural strength reduces 15 ~ 20%, and tensile strength adds 8 ~ 11%, initial elastic modulus reduces 16 ~ 21%, and the reduction of initial elastic modulus shows that the flexibility of ramee strengthens;
(3) the flexibility properties-correcting agent that prepared by the present invention is water-soluble polymer, and not containing objectionable impuritiess such as formaldehyde, total alkali content is low, and preparation process is without the need to heating, and intermediates are without the need to being separated, little on the Final finishing impact of ramee, are convenient to produce and quality control;
(4) preparation method of the present invention is simple to operate, and energy consumption is low, prepares without the need to adopting thermal source, there is the advantages such as energy-conservation, environmental protection, therefore, supple modifier of the present invention and preparation method thereof is applicable to industrialization scale operation, is widely used in ramie weaving mill and weaves other relevant industries to ramie.
Embodiment
Form is described in further detail foregoing of the present invention again by the following examples, but this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
A kind of water-soluble supple modifier for ramee of the present embodiment, described water-soluble supple modifier is prepared from by each raw material of following weight part:
Concentration is the hydrogen peroxide of 0.2mol/L: 10mL
Concentration is the vitamins C aqueous solution of 0.2mol/L: 10mL
Vinylformic acid: 2.3g
Methylpropene sodium sulfonate: 5g
Pure water: 72.7g.
Water-soluble supple modifier for ramee described above adopts following low temperature preparation method to be prepared from, and comprises the steps:
(1) take each component raw material, add 72.7g pure water in there-necked flask, then 2.3g vinylformic acid and 5g methylpropene sodium sulfonate are added respectively in there-necked flask, slowly stir, mix, the temperature controlling solution in flask is 16 DEG C;
(2) under the condition stirred, the vitamins C aqueous solution of to be the hydrogen peroxide of 0.2mol/L and 10mL concentration by 10mL concentration be 0.2mol/L is added drop-wise in step (1) described flask respectively simultaneously, controlling time for adding is 2 hours, after dropwising, continue stirring 3 hours, copolyreaction obtains vinylformic acid-methylpropene sodium sulfonate multipolymer;
(3) sodium hydroxide solution of described for step (2) obtained vinylformic acid-methylpropene sodium sulfonate multipolymer 30wt% is neutralized to pH=7 ~ 8, i.e. the obtained described water-soluble supple modifier for ramee, the solid content of described properties-correcting agent is 10.5%.
Embodiment 2
A kind of water-soluble supple modifier for ramee of the present embodiment, described water-soluble supple modifier is prepared from by each raw material of following weight part:
Concentration is the hydrogen peroxide of 0.2mol/L: 10mL
Concentration is the vitamins C aqueous solution of 0.4mol/L: 10mL
Vinylformic acid: 4.6g
Methylpropene sodium sulfonate: 5g
Pure water: 70.4g.
Water-soluble supple modifier for ramee described above adopts following low temperature preparation method to be prepared from, and comprises the steps:
(1) take each component raw material, add 70.4g pure water in there-necked flask, then 4.6g vinylformic acid and 5g methylpropene sodium sulfonate are added respectively in there-necked flask, slowly stir, mix, the temperature controlling solution in flask is 20 DEG C;
(2) under the condition stirred, the vitamins C aqueous solution of to be the hydrogen peroxide of 0.2mol/L and 10mL concentration by 10mL concentration be 0.4mol/L is added drop-wise in step (1) described flask respectively simultaneously, controlling time for adding is 2 hours, after dropwising, continue stirring 3 hours, copolyreaction obtains vinylformic acid-methylpropene sodium sulfonate multipolymer;
(3) sodium hydroxide solution of described for step (2) obtained vinylformic acid-methylpropene sodium sulfonate multipolymer 30wt% is neutralized to pH=7 ~ 8, i.e. the obtained described water-soluble supple modifier for ramee, the solid content of described properties-correcting agent is 11.1%.
Embodiment 3
A kind of water-soluble supple modifier for ramee of the present embodiment, described water-soluble supple modifier is prepared from by each raw material of following weight part:
Concentration is the hydrogen peroxide of 0.4mol/L: 10mL
Concentration is the vitamins C aqueous solution of 0.4mol/L: 10mL
Vinylformic acid: 6.9g
Methylpropene sodium sulfonate: 5g
Pure water: 68.1g.
Water-soluble supple modifier for ramee described above adopts following low temperature preparation method to be prepared from, and comprises the steps:
(1) take each component raw material, add 68.1g pure water in there-necked flask, then 6.9g vinylformic acid and 5g methylpropene sodium sulfonate are added respectively in there-necked flask, slowly stir, mix, the temperature controlling solution in flask is 10 DEG C;
(2) under the condition stirred, the vitamins C aqueous solution of to be the hydrogen peroxide of 0.4mol/L and 10mL concentration by 10mL concentration be 0.4mol/L is added drop-wise in step (1) described flask respectively simultaneously, controlling time for adding is 2.5 hours, after dropwising, continue stirring 2.5 hours, copolyreaction obtains vinylformic acid-methylpropene sodium sulfonate multipolymer;
(3) sodium hydroxide solution of described for step (2) obtained vinylformic acid-methylpropene sodium sulfonate multipolymer 30wt% is neutralized to pH=7 ~ 8, i.e. the obtained described water-soluble supple modifier for ramee, the solid content of described properties-correcting agent is 12.8%.
Embodiment 4
A kind of water-soluble supple modifier for ramee of the present embodiment, described water-soluble supple modifier is prepared from by each raw material of following weight part:
Concentration is the hydrogen peroxide of 0.4mol/L: 10mL
Concentration is the vitamins C aqueous solution of 0.4mol/L: 10mL
Vinylformic acid: 6.9g
Methylpropene sodium sulfonate: 5g
Pure water: 68.1g.
Water-soluble supple modifier for ramee described above adopts following low temperature preparation method to be prepared from, and comprises the steps:
(1) take each component raw material, add 68.1g pure water in there-necked flask, then 6.9g vinylformic acid and 5g methylpropene sodium sulfonate are added respectively in there-necked flask, slowly stir, mix, the temperature controlling solution in flask is 6 DEG C;
(2) under the condition stirred, the vitamins C aqueous solution of to be the hydrogen peroxide of 0.4mol/L and 10mL concentration by 10mL concentration be 0.4mol/L is added drop-wise in step (1) described flask respectively simultaneously, controlling time for adding is 3 hours, after dropwising, continue stirring 2 hours, copolyreaction obtains vinylformic acid-methylpropene sodium sulfonate multipolymer;
(3) sodium hydroxide solution of described for step (2) obtained vinylformic acid-methylpropene sodium sulfonate multipolymer 30wt% is neutralized to pH=7 ~ 8, i.e. the obtained described water-soluble supple modifier for ramee, the solid content of described properties-correcting agent is 12.5%.
Embodiment 5
A kind of water-soluble supple modifier for ramee of the present embodiment, described water-soluble supple modifier is prepared from by each raw material of following weight part:
Concentration is the hydrogen peroxide of 0.2mol/L: 10mL
Concentration is the vitamins C aqueous solution of 0.4mol/L: 10mL
Vinylformic acid: 9.2g
Methylpropene sodium sulfonate: 5g
Pure water: 65.8g.
Water-soluble supple modifier for ramee described above adopts following low temperature preparation method to be prepared from, and comprises the steps:
(1) take each component raw material, add 65.8g pure water in there-necked flask, then 9.2g vinylformic acid and 5g methylpropene sodium sulfonate are added respectively in there-necked flask, slowly stir, mix, the temperature controlling solution in flask is 18 DEG C;
(2) under the condition stirred, the vitamins C aqueous solution of to be the hydrogen peroxide of 0.2mol/L and 10mL concentration by 10mL concentration be 0.4mol/L is added drop-wise in step (1) described flask respectively simultaneously, controlling time for adding is 2.5 hours, after dropwising, continue stirring 3 hours, copolyreaction obtains vinylformic acid-methylpropene sodium sulfonate multipolymer;
(3) sodium hydroxide solution of described for step (2) obtained vinylformic acid-methylpropene sodium sulfonate multipolymer 30wt% is neutralized to pH=7 ~ 8, i.e. the obtained described water-soluble supple modifier for ramee, the solid content of described properties-correcting agent is 13.1%.
Application test example 1
By water-soluble supple modifier obtained for above-described embodiment 1 for the preparation of modified ramie, described modified ramie adopts following preparation method to obtain:
(1) in uncovered beaker, 5g ramee is immersed in the aqueous sodium hydroxide solution of 100gpH=11, be heated to 60 DEG C, dipping 2h; Then water-soluble supple modifier obtained for 2g embodiment 1 is joined in aqueous sodium hydroxide solution, slowly stir with glass stick and promote that it mixes, again ramee is flooded 2h, stir once every 30min during dipping;
(3) to be impregnated complete after, take out ramee, washing repeatedly, until almost wash the properties-correcting agent being attached to described ramee remained on surface completely off, then by clean after ramee vacuum-drying, namely obtain the ramee that described flexibility is modified.
The ramee of above-mentioned modified ramee and non-modified is carried out tensile strength and flexural strength test respectively, and calculates initial modulus.Result shows, the modified ramee of this application test example is relative to unmodified ramee, and its flexural strength reduces 15.1%, and tensile strength adds 10.4%, and initial elastic modulus reduces 16.6%.
Application test example 2
Water-soluble supple modifier obtained for the 1.5g embodiment of the present invention 2 is used for modification 5g ramee by the method for modifying identical by above-mentioned application test example 1, the ramee that obtained flexibility is modified.
Test by above-mentioned application test example 1 same test, the performance of method of calculation to the ramee of the modified ramee of this application test example and non-modified, calculate, result shows, the modified ramee of this application test example is relative to unmodified ramee, its flexural strength reduces 14.1%, tensile strength adds 9.6%, and initial elastic modulus reduces 12.9%.
Application test example 3
Water-soluble supple modifier obtained for the 1g embodiment of the present invention 3 is used for modification 5g ramee by the method for modifying identical by above-mentioned application test example 1, the ramee that obtained flexibility is modified.
Test by above-mentioned application test example 1 same test, the performance of method of calculation to the ramee of the modified ramee of this application test example and non-modified, calculate, result shows, the modified ramee of this application test example is relative to unmodified ramee, its flexural strength reduces 16.1%, tensile strength adds 10.6%, and initial elastic modulus reduces 18.8%.
Application test example 4
Water-soluble supple modifier obtained for the 0.5g embodiment of the present invention 4 is used for modification 5g ramee by the method for modifying identical by above-mentioned application test example 1, the ramee that obtained flexibility is modified.
Test by above-mentioned application test example 1 same test, the performance of method of calculation to the ramee of the modified ramee of this application test example and non-modified, calculate, result shows, the modified ramee of this application test example is relative to unmodified ramee, its flexural strength reduces 17.1%, tensile strength adds 9.3%, and initial elastic modulus reduces 19.1%.
Application test example 5
Water-soluble supple modifier obtained for the 3g embodiment of the present invention 5 is used for modification 5g ramee by the method for modifying identical by above-mentioned application test example 1, the ramee that obtained flexibility is modified.
Test by above-mentioned application test example 1 same test, the performance of method of calculation to the ramee of the modified ramee of this application test example and non-modified, calculate, result shows, the modified ramee of this application test example is relative to unmodified ramee, its flexural strength reduces 19.8%, tensile strength adds 8.6%, and initial elastic modulus reduces 20.9%.
Claims (10)
1. the water-soluble supple modifier for ramee, it is characterized in that: described water-soluble supple modifier is prepared from by each raw material of following weight percent content: initiator 0.4 ~ 1%, monomer 5 ~ 15%, surplus is water, wherein, described initiator is hydrogen peroxide and vitamins C, and described monomer is vinylformic acid and methylpropene sodium sulfonate.
2. the water-soluble supple modifier for ramee according to claim 1, is characterized in that: described methylpropene sodium sulfonate and acrylic acid mol ratio are 1:1 ~ 4.
3. the water-soluble supple modifier for ramee according to claim 1 and 2, is characterized in that: described hydrogen peroxide and ascorbic mol ratio are 1:1 ~ 2.
4. a low temperature preparation method for the water-soluble supple modifier for ramee according to claim 1, is characterized in that: described method comprises the steps:
(1) take each component raw material, in there-necked flask, add water, then vinylformic acid and methylpropene sodium sulfonate are added in there-necked flask respectively, slowly stir, mix, and make the temperature of solution in flask maintain 5 ~ 20 DEG C;
(2) under the condition stirred, be added drop-wise in step (1) described flask respectively by hydrogen peroxide and the vitamins C aqueous solution, controlling time for adding is 2 ~ 3 hours, after dropwising simultaneously, continue stirring 2 ~ 3 hours, copolyreaction obtains vinylformic acid-methylpropene sodium sulfonate multipolymer;
(3) described for step (2) obtained vinylformic acid-methylpropene sodium sulfonate multipolymer alkali lye is neutralized to pH=7 ~ 8, i.e. the obtained described water-soluble supple modifier for ramee.
5. the low temperature preparation method of the water-soluble supple modifier for ramee according to claim 4, is characterized in that: described methylpropene sodium sulfonate and acrylic acid mol ratio are 1:1 ~ 4.
6. the low temperature preparation method of the water-soluble supple modifier for ramee according to claim 4, is characterized in that: described hydrogen peroxide and ascorbic mol ratio are 1:1 ~ 2.
7. the low temperature preparation method of the water-soluble supple modifier for ramee according to claim 4, is characterized in that: the sodium hydroxide solution of step (3) described alkali lye to be concentration be 30wt%.
8. the modified ramie that water-soluble supple modifier according to claim 3 is obtained, is characterised in that: described modified ramie adopts following preparation method to obtain:
(1) ramee is immersed in the alkali lye of pH=11 ~ 12, be heated to 60 DEG C, flood 2 hours, then in alkali lye, add water-soluble supple modifier according to claim 3, after slowly stirring, ramee is continued dipping 2h;
(2) after having flooded, ramee is taken out, is washed with water to fiber surface without any residual properties-correcting agent, then by the ramee vacuum-drying after washing, obtain the ramee that described flexibility is modified.
9. modified ramie according to claim 8, is characterised in that: the consumption of described water-soluble supple modifier accounts for 1 ~ 8% of ramee weight.
10. modified ramie according to claim 8 or claim 9, is characterised in that: the sodium hydroxide solution of step (2) described alkali lye to be concentration be 30wt%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110725066A (en) * | 2019-10-10 | 2020-01-24 | 黑龙江黑科科技有限责任公司 | Preparation method of hemp fiber bed core and hemp fiber bed core |
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| CN1253613C (en) * | 2002-11-04 | 2006-04-26 | 东华大学 | Ramie fiber and softening modification treatment method of its fabric |
| CN102358763A (en) * | 2011-07-21 | 2012-02-22 | 北京工业大学 | Method for preparing additive for inhibiting side effect of clay |
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| CN1253613C (en) * | 2002-11-04 | 2006-04-26 | 东华大学 | Ramie fiber and softening modification treatment method of its fabric |
| CN102358763A (en) * | 2011-07-21 | 2012-02-22 | 北京工业大学 | Method for preparing additive for inhibiting side effect of clay |
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| CN110725066A (en) * | 2019-10-10 | 2020-01-24 | 黑龙江黑科科技有限责任公司 | Preparation method of hemp fiber bed core and hemp fiber bed core |
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Application publication date: 20151230 |