CN104109986A - Ring-crush enhanced sizing agent for papermaking and preparation method of sizing agent - Google Patents
Ring-crush enhanced sizing agent for papermaking and preparation method of sizing agent Download PDFInfo
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- CN104109986A CN104109986A CN201410316848.5A CN201410316848A CN104109986A CN 104109986 A CN104109986 A CN 104109986A CN 201410316848 A CN201410316848 A CN 201410316848A CN 104109986 A CN104109986 A CN 104109986A
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Abstract
The invention discloses a ring-crush enhanced sizing agent for papermaking and a preparation method of the sizing agent. The method comprises the following steps: preparing commercially available chrome-free hydrolyzed collagen protein powder extracted from leather waste into a solution with certain concentration; after certain conditional preprocessing, enabling the solution to compound with dissolved polyvinyl alcohol; then, adding an allyl monomer, carrying out graft modification under initiation of an initiating agent to prepare a modified collagen emulsion, and applying the modified collagen emulsion to paper for sizing. According to the invention, the solid leather waste is utilized, and meanwhile, a new addition agent is developed for the papermaking industry. With combination of excellent performances of cheap and easily-available collagen and application of the polyvinyl alcohol as a sizing agent and by adding another allyl monomer, the sizing agent is compounded under certain conditions, thus having good performance.
Description
Technical field
The invention belongs to papermaking chemical product Application Areas, be specifically related to a kind of ring and press enhancement mode emulsifying agent and preparation method thereof.
Background technology
In leather-making technology production process, a large amount of solid waste such as skin slag, shavings, buffing powder, skin bit can be produced, and also a large amount of leftover bits and pieces etc. can be produced after making.
In process hides process, lower 30% left and right of only having raw hide of productive rate that is converted into leather.1.7 hundred million skins of China's year operation, by the generation of waste materials that has 1,400,000 tons, these solid waste are deposited in together, can produce larger harm to environment, be also a kind of wastes of resource simultaneously.In these raw materials, contain the collagen that approaches 80%, can extract comprehensive utilization by a series of means.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of ring and presses enhancement mode emulsifying agent and preparation method thereof, and the Hydrolyzed Collagen extracting in leather castoff of take is raw material, reduces the pollution of Leather Solid Waste to environment; Excellent in performance in conjunction with polyvinyl alcohol as sizing agent, adds another kind of vinyl monomer, synthetic sizing agent under certain conditions, and properties of product are good.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of ring is pressed enhancement mode emulsifying agent and preparation method thereof, comprises the following steps:
1) get in the deionized water that the Hydrolyzed Collagen of 1 ~ 10 part is dissolved in 20 ~ 90 parts, be mixed with Hydrolyzed Collagen solution;
2) get in the deionized water that the polyvinyl alcohol of 1 ~ 10 part joins 20 ~ 90 parts, be placed under 95 ℃ of water temperatures, water-bath is dissolved, and is configured to poly-vinyl alcohol solution;
3) by step 2) in the poly-vinyl alcohol solution that is made into all join in the Hydrolyzed Collagen solution of preparing through step 1), under the condition stirring, allow both be thoroughly mixed to form mixed liquor;
4) in above-mentioned steps 3) in be thoroughly mixed to form the vinyl monomer that mixed liquor adds 1 ~ 5 part, start agitator, warming while stirring, then continue slowly to add the redox initiator of 0.1 ~ 1 part, until react completely, be cooled to room temperature, obtain emulsion, obtain sizing agent;
The umber of each material is parts by mass above.
In a preferred embodiment of the invention, described vinyl monomer is a kind of in butyl acrylate, Isooctyl acrylate monomer or ethyl acrylate.
In a preferred embodiment of the invention, the Hydrolyzed Collagen in described step 1) is preferably the Hydrolyzed Collagen that the conventional acid system of commercially available process extracts from leather castoff, and molecular weight is 7000Da.
The quality percent by volume of the Hydrolyzed Collagen solution being mixed with described step 1 in a preferred embodiment of the invention) is 10%-15%.
In a preferred embodiment of the invention, the alcoholysis degree of described polyvinyl alcohol is 86 ~ 89mol%, and the degree of polymerization is 1700-1750.
In a preferred embodiment of the invention, the 0.2%-0.5% that the consumption of described redox initiator is vinyl monomer.
In a preferred embodiment of the invention, described redox initiator is ammonium persulfate/sodium hydrogen sulfite system.
In a preferred embodiment of the invention, the Hydrolyzed Collagen solution in step 1) is carried out to preliminary treatment, then remove by filter the impurity in collagen.
In a preferred embodiment of the invention, described pretreatment mode is that pretreatment mode is ultrasonic wave or microwave treatment, processing time 10min-60min.
In a preferred embodiment of the invention, described pretreatment mode is the pH value by acid or alkali regulation system, and the scope of pH is 4 ~ 9.
By technique scheme, the invention has the beneficial effects as follows:
1) to take the Hydrolyzed Collagen extracting in leather castoff be raw material in the present invention, abundant raw materials, and cost is lower, and is easily degraded; In emulsion polymerization process, collagen self can be made emulsifying agent, does not need to add in addition initator, has avoided emulsifying agent to have a negative impact to sizing agent performance;
2) PVA(polyvinyl alcohol) be unique can be by bacterium the polyvinyl as carbon source and using energy source, under the effect of bacterium and enzyme, within 46 days, degradable 75%, belongs to a kind of Biodegradable polymer material, can be by Non oil-based route large-scale production, cheap;
As sizing agent, there is the advantage of performances such as can improving printability, ink anchorage, wax anchorage, surface smoothness, glossiness, resistance to ag(e)ing, lining folding degree, lining water-based, lining oiliness, the broken degree of lining, lining fluffing performance simultaneously.
3) the present invention produces sizing agent with the collagen extracting in leather castoff, has reduced on the one hand the pollution of Leather Solid Waste to environment, simultaneously also for paper industry has been developed a kind of new auxiliary agent.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, to the accompanying drawing of required use in embodiment or description of the Prior Art be briefly described below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skills, do not paying under the prerequisite of creative work, can also obtain according to these accompanying drawings other accompanying drawing.
Fig. 1 is preparation flow figure of the present invention.
The specific embodiment
For technological means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, below in conjunction with concrete diagram, further set forth the present invention.
With reference to Fig. 1, a kind of ring is pressed enhancement mode emulsifying agent and preparation method thereof, comprises the following steps:
1) get in the deionized water that the Hydrolyzed Collagen of 1 ~ 10 part is dissolved in 20 ~ 90 parts, be mixed with Hydrolyzed Collagen solution;
Hydrolyzed Collagen solution in step 1) is carried out to preliminary treatment, then remove by filter the impurity in collagen;
Pretreatment mode is that pretreatment mode is ultrasonic wave or microwave treatment, processing time 10min-60min;
Or pretreatment mode is the pH value by acid or alkali regulation system, and wherein acid can be sulfuric acid, hydrochloric acid or acetic acid, and alkali can make NaOH, and the scope of pH is 4 ~ 9;
Pretreatment mode: the molecular weight distribution of Hydrolyzed Collagen is wider, by above-mentioned pretreatment mode, utilize the mode of machinery or physics, suitably reduce molecular weight, allow the molecular weight distribution of collagen concentrate, have like this stability and the effect of utilizing synthetic sizing agent.
Wherein Hydrolyzed Collagen is preferably the Hydrolyzed Collagen that the conventional acid system of commercially available process extracts from leather castoff, and molecular weight is 7000Da; The mass fraction of the Hydrolyzed Collagen solution being mixed with in this step 1) is 10%-15%.
2) get in the deionized water that the polyvinyl alcohol of 1 ~ 10 part joins 20 ~ 90 parts, be placed under 95 ℃ of water temperatures, 30min is dissolved in water-bath, takes out standingly, treats that solution is cooling, removes by filter not dissolved substance wherein, is configured to poly-vinyl alcohol solution; Wherein the alcoholysis degree of polyvinyl alcohol is 86 ~ 89mol%, and the degree of polymerization is 1700-1750;
3) by step 2) in the poly-vinyl alcohol solution that is made into all join in the Hydrolyzed Collagen solution of preparing through step 1), under the condition stirring, allow both be thoroughly mixed to form mixed liquor;
4) in above-mentioned steps 3) in be thoroughly mixed to form the vinyl monomer that mixed liquor adds 1 ~ 5 part, start agitator, warming while stirring, when temperature is elevated to 65 ~ 75 ℃, then slowly add the redox initiator of 0.1 ~ 1 part, 30 ~ 60min adds, until react completely, be cooled to room temperature, obtain emulsion, emulsion color is white or light yellow emulsion; This emulsion is sizing agent; The umber of each material is parts by mass above;
The 0.2%-0.5% that in this step, the consumption of redox initiator is vinyl monomer; Concrete redox initiator is ammonium persulfate/sodium hydrogen sulfite system.
The vinyl monomer wherein adding in step 4) is soft monomer, can butyl acrylate, a kind of in Isooctyl acrylate monomer or ethyl acrylate; The increase of after utilizing the synthetic sizing agent of this vinyl monomer for paper sizing, ring being pressed is obvious.
embodiment 1:
Compound concentration is 10%(w/v) Hydrolyzed Collagen solution 100mL, remove by filter impurity wherein, with certain density acetum, regulating its pH is 5.5, joins in 250mL there-necked flask;
Compound concentration is 1%(w/v) polyvinyl alcohol 100mL, remove by filter wherein undissolved impurity, then join in above-mentioned there-necked flask;
Take butyl acrylate 1g and join in there-necked flask, start agitator, warming while stirring, after temperature rising is 75 ℃, adds 0.10g ammonium persulfate and 0.10g sodium hydrogensulfite to make initator.
Initator half an hour class drip off, initator drips off rear continuation reaction and after two hours, stops heating, and reaction unit is shifted out to water-bath, continues to be cooled to room temperature, obtains emulsion, standby.
Make as stated above sizing agent emulsion, the fluting medium of Dui Mou paper plant carries out applying glue separately, tests its sizing efficiency, finds to be 10.76% to the increment rate of its tensile index, to the increment rate of its ring crush index, is 27.5%, Cobb
60the absorption value reduction rate of (paper of unit are was at 60 seconds systemic biodiversities) is 10%.
embodiment 2:
Compound concentration is 10%(w/v) Hydrolyzed Collagen solution 100mL, remove by filter impurity wherein, join in 250mL there-necked flask.
Compound concentration is 2%(w/v) polyvinyl alcohol 100mL, remove by filter wherein undissolved impurity, then join in above-mentioned there-necked flask, taking butyl acrylate 4g joins in there-necked flask, start agitator, warming while stirring, after temperature rising is 75 ℃, adds 0.14g ammonium persulfate and 0.14g sodium hydrogensulfite to make initator.
Initator half an hour class drip off.Initator drips off rear continuation reaction and after two hours, stops heating, and reaction unit is shifted out to water-bath, continues to be cooled to room temperature, obtains emulsion, standby.
Make as stated above sizing agent emulsion, the fluting medium of Dui Mou paper plant carries out applying glue separately, tests its sizing efficiency, finds to be 9.71% to the increment rate of its tensile index, to the increment rate of its ring crush index, is 29.93%, Cobb
60absorption value reduction rate be 7%.
embodiment 3:
Compound concentration is 15%(w/v) Hydrolyzed Collagen solution 100mL, utilize ultrasonic wave to carry out the ultrasonic 30min of discontinuity to it, remove by filter impurity wherein, with certain density acetum, regulating its pH is 6.0.
To be added in 250mL there-necked flask through pretreated Hydrolyzed Collagen solution.Compound concentration is 5%(w/v) polyvinyl alcohol 100mL, remove by filter wherein undissolved impurity, then join in above-mentioned there-necked flask.
Take butyl acrylate 5g and join in there-necked flask, start agitator, warming while stirring, after temperature rising is 75 ℃, warming while stirring, after temperature rising is 75 ℃, adds 0.4g ammonium persulfate and 0.4g sodium hydrogensulfite to make initator.
Initator half an hour class drip off.Initator drips off rear continuation reaction and after two hours, stops heating, and reaction unit is shifted out to water-bath, continues to be cooled to room temperature, obtains emulsion, standby.
Make as stated above sizing agent emulsion, the fluting medium of Dui Mou paper plant carries out applying glue separately, tests its sizing efficiency, finds to be 2.91% to the increment rate of its tensile index, to the increment rate of its ring crush index, is 20.2%, Cobb
60absorption value reduction rate be 8%.
More than show and described basic principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and description, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (10)
1. a ring is pressed enhancement mode emulsifying agent and preparation method thereof, it is characterized in that, comprises the following steps:
1) get in the deionized water that the Hydrolyzed Collagen of 1 ~ 10 part is dissolved in 20 ~ 90 parts, be mixed with Hydrolyzed Collagen solution;
2) get in the deionized water that the polyvinyl alcohol of 1 ~ 10 part joins 20 ~ 90 parts, be placed under 95 ℃ of water temperatures, water-bath is dissolved, and is configured to poly-vinyl alcohol solution;
3) by step 2) in the poly-vinyl alcohol solution that is made into all join in the Hydrolyzed Collagen solution of preparing through step 1), under the condition stirring, allow both be thoroughly mixed to form mixed liquor;
4) in above-mentioned steps 3) in be thoroughly mixed to form the vinyl monomer that mixed liquor adds 1 ~ 5 part, start agitator, warming while stirring, then continue slowly to add the redox initiator of 0.1 ~ 1 part, until react completely, be cooled to room temperature, obtain emulsion, obtain sizing agent;
The umber of each material is parts by mass above.
2. a kind of ring according to claim 1 is pressed enhancement mode emulsifying agent and preparation method thereof, it is characterized in that, described vinyl monomer is a kind of in butyl acrylate, Isooctyl acrylate monomer or ethyl acrylate.
3. a kind of ring according to claim 1 is pressed enhancement mode emulsifying agent and preparation method thereof, it is characterized in that, Hydrolyzed Collagen in described step 1) is preferably the Hydrolyzed Collagen that the conventional acid system of commercially available process extracts from leather castoff, and molecular weight is 7000Da.
4. a kind of ring according to claim 1 is pressed enhancement mode emulsifying agent and preparation method thereof, it is characterized in that described step 1) in the quality percent by volume of the Hydrolyzed Collagen solution that is mixed be 10%-15%.
5. a kind of ring according to claim 1 is pressed enhancement mode emulsifying agent and preparation method thereof, it is characterized in that, the alcoholysis degree of described polyvinyl alcohol is 86 ~ 89mol%, and the degree of polymerization is 1700-1750.
6. a kind of ring according to claim 1 is pressed enhancement mode emulsifying agent and preparation method thereof, it is characterized in that the 0.2%-0.5% that the consumption of described redox initiator is vinyl monomer.
7. a kind of ring according to claim 1 is pressed enhancement mode emulsifying agent and preparation method thereof, it is characterized in that, described redox initiator is ammonium persulfate/sodium hydrogen sulfite system.
8. a kind of ring according to claim 1 is pressed enhancement mode emulsifying agent and preparation method thereof, it is characterized in that, the Hydrolyzed Collagen solution in step 1) is carried out to preliminary treatment, then removes by filter the impurity in collagen.
9. a kind of ring according to claim 8 is pressed enhancement mode emulsifying agent and preparation method thereof, it is characterized in that, described pretreatment mode is that pretreatment mode is ultrasonic wave or microwave treatment, processing time 10min-60min.
10. a kind of ring according to claim 8 is pressed enhancement mode emulsifying agent and preparation method thereof, it is characterized in that, described pretreatment mode is the pH value by acid or alkali regulation system, and the scope of pH is 4 ~ 9.
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| CN201410316848.5A CN104109986B (en) | 2014-07-04 | 2014-07-04 | A kind of ring pressure enhancement mode emulsifying agent and preparation method thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964537A (en) * | 2012-11-12 | 2013-03-13 | 陕西科技大学 | Method for preparing surface sizing agent emulsion through utilizing tanning wastes |
| CN103669109A (en) * | 2013-12-13 | 2014-03-26 | 陕西科技大学 | Preparation method for paper-making sizing agent |
| CN103757983A (en) * | 2014-02-17 | 2014-04-30 | 陕西科技大学 | Modified hydrolyzed collagen solid sizing agent and preparing method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102964537A (en) * | 2012-11-12 | 2013-03-13 | 陕西科技大学 | Method for preparing surface sizing agent emulsion through utilizing tanning wastes |
| CN103669109A (en) * | 2013-12-13 | 2014-03-26 | 陕西科技大学 | Preparation method for paper-making sizing agent |
| CN103757983A (en) * | 2014-02-17 | 2014-04-30 | 陕西科技大学 | Modified hydrolyzed collagen solid sizing agent and preparing method thereof |
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