CN108611920A - A kind of preparation method of pulping and paper-making inorfil reinforcing agent - Google Patents
A kind of preparation method of pulping and paper-making inorfil reinforcing agent Download PDFInfo
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- CN108611920A CN108611920A CN201810546184.XA CN201810546184A CN108611920A CN 108611920 A CN108611920 A CN 108611920A CN 201810546184 A CN201810546184 A CN 201810546184A CN 108611920 A CN108611920 A CN 108611920A
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Classifications
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
-
- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/38—Inorganic fibres or flakes siliceous
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
Abstract
The invention discloses a kind of preparation methods of pulping and paper-making inorfil reinforcing agent, and with starch, styrene, butyl acrylate is raw material, prepare a kind of novel inorganic fiber reinforcing agent by emulsion polymerisation process, synthesis material dosage is:10 parts by weight of starch, 10 ~ 18 parts by weight of styrene, 2 ~ 10 parts by weight of butyl acrylate.Reinforcing agent is used for flyash/gangue fiber surface, reaches the humidification to fiber, can so that flyash/bastard coal mineral wool in paper-making industry, plant fiber can be saved, additionally it is possible to reduce the pulping process produced pollution, reduce papermaking cost.
Description
Technical field
The present invention relates to pulp technology for making paper, and in particular to a kind of inorfil reinforcing agent.
Background technology
With the continuous development of modern humans' civilization, paper has been increasingly becoming the fields such as industry, agricultural, business, construction industry
Indispensable material, and it is not exclusively limited only to the use of the culture fields such as writing, paper requirements amount is also rising year by year.It is many
It is well known, paper, cardboard raw material be mainly plant fiber, and just contain a large amount of plant fiber in trees, therefore to trees
It is a large amount of felling so that China forest cover face is fallen sharply so that animal lose habitat, soil sandification, weather be deteriorated, serious shadow
Demand degree of the ecological balance in the China Xiang Liao due to different field to paper various aspects of performance is different, merely with plant fiber
Copy paper cannot be satisfied specific demand of the people to paper performance.Therefore, it is obtained in recent years using inorfil paper technology
Faster development.
The country has relevant report reflection flyash/bastard coal mineral wool to have similarity in shape with plant fiber at present,
Treated flyash/gangue fibre whiteness can reach 76 DEG C,(It is 54 that national standard, which limits electro-photographic paper highest whiteness,
DEG C, it is 94 DEG C that national standard, which limits uncoated Cultural Paper highest whiteness,), therefore, flyash/bastard coal mineral wool can be used as one kind
Very friendly fiber carries out mixing papermaking with plant fiber.But since flyash/bastard coal mineral wool belongs to inorfil, have
The disadvantage that brittleness is big, intensity is low, directly in application, can be only applied to the paper pulp filler material of papermaking or answered instead of Activities of Some Plants fiber
For cardboard, low-grade wrapping paper.If flyash/bastard coal mineral wool is modified processing, it will greatly improve it in papermaking
The application range and range of aspect.The present invention is with starch, and styrene, butyl acrylate is raw material, by emulsion polymerisation process system
For a kind of novel inorganic fiber reinforcing agent is gone out, reinforcing agent is used for flyash/gangue fiber surface, reaches the increasing to fiber
Pretend use, can so that flyash/bastard coal mineral wool in paper-making industry, plant fiber can be saved, additionally it is possible to reduce slurrying
The journey produced pollution reduces papermaking cost.
Invention content
The purpose of the present invention is to provide a kind of preparation method of pulping and paper-making inorfil reinforcing agent, the reinforcing agents
Flyash/gangue fiber surface can be modified, change the shortcomings that its rigidity is strong, brittleness is big, easy fracture.
A kind of preparation method of pulping and paper-making inorfil reinforcing agent, it is characterised in that this method includes following step
Suddenly:
10 weight starch, 0.5 parts by weight sodium hydrogensulfite, 0.02 parts by weight of ferrous sulfate are taken to be added to reaction kettle at room temperature
In, 70 parts by weight of deionized water are added, solution is to slowly warm up to 90 DEG C ~ 95 DEG C, continues constant temperature magnetic force by magnetic agitation 30min
50min is stirred, starch is made fully to be gelatinized.The starch of above-mentioned gelatinization is cooled to 80 DEG C or so, be added 20 parts by weight of styrene and
2.5 parts by weight hydrogen peroxide are slowly added dropwise in Butyl Acrylate Monomer after stirring evenly, 1.5 ~ 2 h are added dropwise, and add 8 weight
Part functionalization MOF-SO3@KIT-6 nanometer bodies, constant temperature is stirred to react 90 min at 80 DEG C, discharges to get novel inorganic fiber
With reinforcing agent reinforcing agent.
Advantageous effect:The present invention provides a kind of preparation method of pulping and paper-making inorfil reinforcing agent, passes through starch
Reinforcing agent is adsorbed in fiber surface, forms one layer of adsorbed film by the suction-operated to flyash/bastard coal mineral wool, to reach fine
The humidification of dimension.In addition functionalization MOF-SO3 KIT-6 Nanostructured bulks are added in preparation process, are added lower
Polymer physics, chemistry and mechanical property are just remarkably improved under amount, the two synergistic effect can increase substantially flyash/bastard coal
The enhancing of mineral wool is modified.
Specific implementation mode
Embodiment 1
10 weight starch, 0.5 parts by weight sodium hydrogensulfite, 0.02 parts by weight of ferrous sulfate are taken to be added to reaction kettle at room temperature
In, 70 parts by weight of deionized water are added, solution is to slowly warm up to 90 DEG C ~ 95 DEG C, continues constant temperature magnetic force by magnetic agitation 30min
50min is stirred, starch is made fully to be gelatinized.The starch of above-mentioned gelatinization is cooled to 80 DEG C or so, 13 parts by weight of styrene and 7 are added
Parts by weight propylene acid butyl ester monomer, is slowly added dropwise 2.5 parts by weight hydrogen peroxide after stirring evenly, 1.5 ~ 2 h are added dropwise, add
8 parts by weight functionalization MOF-SO3@KIT-6 nanometer bodies, constant temperature is stirred to react 90 min at 80 DEG C, discharges to get novel nothing
Machine fiber reinforcing agent reinforcing agent.
KIT-6 nanometers of preparations of above-mentioned functionalization MOF-SO3 are as follows:
5 parts by weight xanthans, 2 parts by weight tetradecy lamines are taken to be dissolved in 15 parts by weight of ethanol, it is molten that magnetic agitation 1h obtains dispersant
Liquid.Solution is sprayed into 50ml/min spray rates in the MOF-SO3@KIT-6 nanometer bodies of 10 parts by weight high-speed stirreds, stirring
Rate is 1000 turns/min, and mixture is transferred in reaction kettle after stirring, in nitrogen atmosphere, 80 ~ 90 DEG C, and under 0.5kPa
With 500 ~ 600 turns/min stirring 12h to get to functionalization MOF-SO3@KIT-6 nanometer bodies.
Above-mentioned MOF-SO3 KIT-6 nanometers of preparations are as follows:20 parts of KIT-6 powder ultrasonics are taken to be dispersed in 30 parts, N-
N-dimethylacetylamide(DMA)In, 45 parts of hydration zirconium oxychlorides are then weighed respectively and 6 part of 2-sulfonic acid para-phthalic sodium adds
Enter in above-mentioned dispersion liquid, then add 9 parts of formic acid, ultrasonic disperse 310min is transferred them in polytetrafluoroethyllining lining, covered
Lid and being put into reaction kettle seals close, is subsequently placed in sustained response 14h in 150 DEG C of constant temperature oven, reaction product is led to
It crosses and centrifuges out, first cleaned 3 times with fresh DMF solvent, then repeatedly washed with fresh alcohol solvent, centrifuge production
Object, which is finally placed in 50 DEG C of baking oven, keeps 6h, that is, obtains MOF-SO3@KIT-6 composite nanometre powders.
Embodiment 2
Identical with embodiment 1, difference is:18 parts by weight of styrene and 2 parts by weight propylene acid butyl ester monomers are added.
Embodiment 3
Identical with embodiment 1, difference is:17 parts by weight of styrene and 3 parts by weight propylene acid butyl ester monomers are added.
Embodiment 4
Identical with embodiment 1, difference is:16 parts by weight of styrene and 4 parts by weight propylene acid butyl ester monomers are added.
Embodiment 5
Identical with embodiment 1, difference is:15 parts by weight of styrene and 5 parts by weight propylene acid butyl ester monomers are added.
Embodiment 6
Identical with embodiment 1, difference is:14 parts by weight of styrene and 6 parts by weight propylene acid butyl ester monomers are added.
Embodiment 7
Identical with embodiment 1, difference is:12 parts by weight of styrene and 8 parts by weight propylene acid butyl ester monomers are added.
Embodiment 8
Identical with embodiment 1, difference is:11 parts by weight of styrene and 9 parts by weight propylene acid butyl ester monomers are added.
Embodiment 9
Identical with embodiment 1, difference is:10 parts by weight of styrene and 10 parts by weight propylene acid butyl ester monomers are added.
Comparative example 1
Identical with embodiment 1, difference is:Only it is added without functionalization MOF-SO3@KIT-6 nanometer bodies.
Comparative example 2
Identical with embodiment 1, difference is:What is be only added is untreated MOF-SO3@KIT-6 nanometer bodies.
Comparative example 3
Identical with embodiment 1, difference is:It is added without 14 when only preparing functionalization MOF-SO3@KIT-6 nanometer bodies
Amine.
Comparative example 4
Identical with embodiment 1, difference is:It is added without xanthan when only preparing functionalization MOF-SO3@KIT-6 nanometer bodies
Glue.
Comparative example 5
Identical with embodiment 1, difference is:It is not interposing at nitrogen when only preparing functionalization MOF-SO3@KIT-6 nanometer bodies
In atmosphere.
Comparative example 6
Identical with embodiment 1, difference is:It is added without ferrous sulfate when only preparing inorfil reinforcing agent.
Comparative example 7
Identical with embodiment 1, difference is:It is added without butyl acrylate when only preparing inorfil reinforcing agent.
Comparative example 8
Identical with embodiment 1, difference is:It is added without styrene when only preparing inorfil reinforcing agent.
Comparative example 9
Identical with embodiment 1, difference is:2 parts by weight hydrogen peroxide are added when only preparing inorfil reinforcing agent,
1 parts by weight sodium hydrogensulfite.
The inorfil prepared as follows to the embodiment of the present invention 1 ~ 9 and comparative example 1 ~ 9 carries out performance with reinforcing agent
Test:1, the enhancing of flyash/bastard coal mineral wool is modified
It weighs 99 g water to be placed in beaker, the enhancing agent emulsion of 1 g is added thereto, fully shakes up, adds the fine coal of 2 g
Ash/bastard coal mineral wool, the stir speed (S.S.) using 50 r/min make it be uniformly dispersed, and after standing 1 h, suction filtration obtains enhancing modified
Flyash/bastard coal mineral wool, then will enhancing flyash/bastard coal mineral wool be put into baking oven and be dried for standby.
2, fiber-reinforced modified effect assessment
By reinforcing fiber, drying to constant weight, weighs the reinforcing fiber of 50g in mortar, grinds 80 times, and 120 mesh are sieved 60 times, claims
The quality of remaining reinforcing fiber, calculates its sieving rate after amount sieving.
Sieving rate %=(M0-M)/M0×100%
In formula:M0The dry weight of fiber before-sieving(g);The dry weight of residual fiber after M-sieving(g).
Inorfil reinforcing agent Evaluation results
As seen from the above table, using the inorfil prepared under the conditions of embodiment 1 flyash/bastard coal mineral wool is acted on reinforcing agent
When its sieving rate it is minimum, remaining embodiment effect unobvious illustrates that the reinforcing agent enhancing effect prepared under the conditions of embodiment 1 exceeds
That expects is good, when styrene and constant Butyl Acrylate Monomer total amount, with the change of monomer ratio dosage, flyash/coal
The sieving of spoil fiber takes the lead in increasing after reducing, the possible reason is as monomer weight ratio is higher, flyash/bastard coal mineral wool table
The film toughness that bread covers increases, but when mass ratio is excessively high, and excessive styrene is unfavorable for enhancing agent emulsion on fiber
Good filming, therefore sieving rate is on a declining curve.In addition the addition of 1 ~ 5 functions MOF-SO3@KIT-6 nanometer bodies of comparative example
And its parts by weight are affected to the enhancing performance of reinforcing agent, comparative example 5 ~ 9 illustrates to prepare former when inorfil reinforcing agent
The selection of material and the selection of condition have prominent influence to reinforcing agent performance.
Claims (5)
1. a kind of preparation method of pulping and paper-making inorfil reinforcing agent, it is characterised in that this approach includes the following steps:
10 weight starch, 0.5 parts by weight sodium hydrogensulfite, 0.02 parts by weight of ferrous sulfate are taken to be added to reaction kettle at room temperature
In, 70 parts by weight of deionized water are added, solution is to slowly warm up to 90 DEG C ~ 95 DEG C, continues constant temperature magnetic force by magnetic agitation 30min
Stir 50min, starch made fully to be gelatinized, the starch of above-mentioned gelatinization is cooled to 80 DEG C or so, be added 20 parts by weight of styrene and
2.5 parts by weight hydrogen peroxide are slowly added dropwise in Butyl Acrylate Monomer after stirring evenly, 1.5 ~ 2 h are added dropwise, and add 8 weight
Part functionalization MOF-SO3@KIT-6 nanometer bodies, constant temperature is stirred to react 90 min at 80 DEG C, discharges to get novel inorganic fiber
With reinforcing agent reinforcing agent.
2. a kind of preparation method of pulping and paper-making inorfil reinforcing agent according to claim 1, it is characterised in that on
It is 200 ~ 300r/min to state mixing speed in step.
3. a kind of preparation method of pulping and paper-making inorfil reinforcing agent according to claim 1, it is characterised in that on
It is 9 to state styrene and butyl acrylate mass ratio in step:1~1:1.
4. a kind of preparation method of pulping and paper-making inorfil reinforcing agent according to claim 1, it is characterised in that on
It is ceramic electric heating reaction kettle to state reaction kettle in step.
5. a kind of preparation method of pulping and paper-making inorfil reinforcing agent according to claim 1, it is characterised in that on
It is as follows to state KIT-6 nanometers of preparations of functionalization MOF-SO3 described in step:
20 parts of KIT-6 powder ultrasonics are taken to be dispersed in 30 parts, N-N-dimethylacetylamide(DMA)In, 45 parts of water are then weighed respectively
It closes zirconium oxychloride and 6 part of 2-sulfonic acid para-phthalic sodium is added in above-mentioned dispersion liquid, then add 9 parts of formic acid, ultrasonic disperse
30min is transferred them in polytetrafluoroethyllining lining, is covered lid and is put into reaction kettle and seals close, is subsequently placed in 150 DEG C
Constant temperature oven in sustained response for 24 hours, by reaction product by centrifuge come out, first cleaned 3 times with fresh DMF solvent,
It is repeatedly washed with fresh alcohol solvent again, centrifugation product, which is finally placed in 50 DEG C of baking oven, keeps 6h, that is, obtains MOF-
SO3@KIT-6 composite nanometre powders,
5 parts by weight xanthans, 2 parts by weight tetradecy lamines are taken to be dissolved in 15 parts by weight of ethanol, it is molten that magnetic agitation 1h obtains dispersant
Solution is sprayed into the MOF-SO of 10 parts by weight high-speed stirreds by liquid with 50ml/min spray rates3@KIT-6 composite nanometre powders
In, stir speed (S.S.) is 1000 turns/min, and mixture is transferred in reaction kettle after stirring, in nitrogen atmosphere, 80 ~ 90 DEG C,
With 500 ~ 600 turns/min stirring 12h to get to functionalization MOF-SO under 0.5kPa3@KIT-6 nanometer bodies.
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113174114A (en) * | 2021-05-27 | 2021-07-27 | 长治市宏瑞祥环保科技有限公司 | Method for preparing polyvinyl chloride carbon plastic product by using coal gangue |
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WO2012150863A1 (en) * | 2011-05-04 | 2012-11-08 | Stichting Sanquin Bloedvoorziening | Means and methods to determine a risk of multiple organ failure |
CN104718214A (en) * | 2012-05-31 | 2015-06-17 | 国立科学研究中心 | Improved organic-inorganic hybrid solid having a modified outer surface |
CN106543461A (en) * | 2016-12-06 | 2017-03-29 | 复旦大学 | MOF‑SO3H@GO modified polymer hybrid PEM and preparation method thereof |
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2018
- 2018-05-31 CN CN201810546184.XA patent/CN108611920B/en active Active
Patent Citations (4)
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WO2012150863A1 (en) * | 2011-05-04 | 2012-11-08 | Stichting Sanquin Bloedvoorziening | Means and methods to determine a risk of multiple organ failure |
CN102635019A (en) * | 2012-04-16 | 2012-08-15 | 陕西科技大学 | Preparation method of organic silicon surface sizing agent |
CN104718214A (en) * | 2012-05-31 | 2015-06-17 | 国立科学研究中心 | Improved organic-inorganic hybrid solid having a modified outer surface |
CN106543461A (en) * | 2016-12-06 | 2017-03-29 | 复旦大学 | MOF‑SO3H@GO modified polymer hybrid PEM and preparation method thereof |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113174114A (en) * | 2021-05-27 | 2021-07-27 | 长治市宏瑞祥环保科技有限公司 | Method for preparing polyvinyl chloride carbon plastic product by using coal gangue |
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