CN101165269A - Preparation method for producing aramid fiber paper by using thermoplastic fiber as adhesive - Google Patents
Preparation method for producing aramid fiber paper by using thermoplastic fiber as adhesive Download PDFInfo
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- CN101165269A CN101165269A CNA2006100220825A CN200610022082A CN101165269A CN 101165269 A CN101165269 A CN 101165269A CN A2006100220825 A CNA2006100220825 A CN A2006100220825A CN 200610022082 A CN200610022082 A CN 200610022082A CN 101165269 A CN101165269 A CN 101165269A
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Abstract
The present invention is process of making aramid fiber paper with thermoplastic fiber as the adhesive. The aramid fiber paper consists of aramid fiber in 50-80 weight portions and adhering thermoplastic fiber in 20-50 weight portions. It is made that hydraulically disintegrating aramid fiber and thermoplastic fiber separately to form aramid fiber pulp and thermoplastic fiber pulp of 0.06 wt% concentration, mixing two kinds of pulp in the required ratio in a pulp compounding kettle, making paper in a common paper making machine, dewatering, pre-drying, hot rolling in a hot rolling machine to obtain paper product. The temperature in the baking channel is controlled in 10-50 deg.c over the smelting point of the adhering thermoplastic fiber, and the temperature in the hot roller is controlled in 30-50 deg.c over the smelting point. Adopting thermoplastic fiber as the adhesive can simplify the production process, reduce pollution and raise the fireproof performance of the paper.
Description
Affiliated technical field
The invention belongs to the speciality paper production field.
Background technology
At present, domestic and international disclosed aramid fiber paper all is to be raw material with Fanglun 1313 (Nomex) (seeing United States Patent (USP) 5667900,3756908) and Fanglun 1414 (Kevlar) (seeing United States Patent (USP) 6942757,6319605) respectively, or is that raw material makes (seeing United States Patent (USP) 6407017,6319605) with these two kinds of fiber hybrid fibers.Because the aramid fiber paper made from above-mentioned raw materials has intensity height, high temperature resistant, corrosion-resistant, advantage such as electrical insulation capability is good, at electronics, electrical equipment, fields such as space flight, aviation are widely used as high temperature insulating material, cellular structural material.Therefore, be subjected to various countries researcher's attention, and have a large amount of patents to deliver.In these patents, nearly all adopt above-mentioned twice-laid staple fibre, pulp, fibrid and the papermaking of low molecule aramid fiber resin gel.Wherein, fibrid and low molecule aramid fiber resin gel mainly play binder.Yet, owing to also be restricted by the performance of restriction (tensile strength is less than 3.2Gpa, and modulus is less than 90Gpa, and limited oxygen index is less than 30%, the water absorption rate 5-6% of fiber) the aramid fiber paper of above-mentioned fibre property.Also undesirable aspect anti-combustion, anti-hydrolysis, endurance, UV resistant.Striving for reaching more also unsatisfactory aspect the high strength.In Chinese patent (application number is 99114635.2), disclosed the method for making binder manufacturing Fanglun 1414 paper of polyethylene terephthalate.Though reducing aspect the water absorption rate and the aspect that reduces production costs has obtained certain progress, effect is poorer aspect fire-retardant, high temperature resistant, and the elongation at break of paper low (2-3%) can not satisfy the needs of doing the insulation material.In Chinese patent (application number is 200510035261.8), disclosed a kind of method with PPTA pulp, fibrid production Fanglun 1414 paper, and in paper-making process, introduced the technology of the surface of paper being handled with the sulfuric acid solution of PPTA, not only make paper technology more complicated but also increased environmental pollution.
Summary of the invention
Make the manufacture method that binder is produced aramid fiber paper with thermoplastic fibre, this fibrous paper contains:
Aramid fiber 50-80 weight portion
Thermoplasticity is cohered fiber 20--50 weight portion;
Behind the aramid fiber cutting short-forming fiber, discongest in the waterpower fluffer by 0.06% weight concentration and to make slurries (A), thermoplasticity is cohered fiber discongest in the waterpower fluffer by 0.06% weight concentration and make slurries (B); Slurries (A), (B) are joined by described weight portion join in the slurry still, add the modulation of suitable conventional dispersant and thickener and obtain paper pulp, shapings of manufacturing paper with pulp on the paper machine that the slurries after preparing are general dewatered, and be predrying.Ground paper after predrying passes through from drying tunnel, and further on heat bundle machine heat be bundled into type and obtain finished paper; Drying tunnel temperature is controlled at thermoplasticity and coheres the above 10-50 of fiber fusing point ℃, and heat bundle roll temperature is controlled at and coheres the following 30-50 of fiber fusing point ℃; Heat is pricked the line pressure 500-3000cN/cm of roller.
The present invention adopts PPS thermoplastic fibres such as (polyphenylene sulfides) to make binder, has improved fire resistance and anti-hydrolytic performance, insulating properties and the mechanical strength of paper.In addition, the fiber of two kinds of fibrillation weave in disorderly when copying paper, after hot pressing, the polyester fiber fusion is bonded together aramid fiber, has fundamentally solved aramid fiber and polyester fiber and has cohered bad problem.Avoided to use other binder at compound tense, thereby simplified manufacturing technique at aramid fiber and polyester fiber.In paper-making process, do not need to add common paper pulp, water can be recycled, pollution-free to environment; And can at random add other fiber and auxiliary agent as required, make the composite sheet of various different performances.
In order to prevent that thermoplastic fibre from hot high pressure bundle process roll banding taking place, adopt earlier blank paper to be preheating in drying tunnel more than the softening point that coheres fiber, carry out hot high pressure below the softening point that coheres fiber and prick being lower than again.
The specific embodiment
Below in conjunction with embodiment technology of the present invention is described in further detail.
Embodiment 1
The proportioning of aromatic heterocyclic modified aramid fiber/polyphenylene sulfide fibre composite paper is:
Aromatic heterocyclic modified aramid fiber (5-6mm) 60 weight portions
Polyphenylene sulfide fibre (3-6mm) 40 weight portions
In 0.2 mole p-phenylenediamine (PPD), 0.6 mole chloro p-phenylenediamine (PPD), 0.2 mole 2-(4 aminophenyl)-5 (6) aminophenyl benzimidazoles and the ratio of 1.01 moles of paraphthaloyl chloride reactions, with above-mentioned reactant, at NMP/CaCl
2Carry out the low temperature solution polymerization reaction in the dicyandiamide solution and generate resin solution.Directly make pristine fibre by wet spinning then with resin solution.Spinnerets 300 holes, aperture 0.08mm spins 20 meters/minute of speed.Precursor carries out hot drawing-off under 350 ℃ of conditions under nitrogen protection, the short at last staple fibre that length is the 5-6 millimeter, the fiber number 2.0D of being cut into
Above-mentioned staple fibre discongested in the waterpower fluffer by 0.06% weight concentration make slurries (A).Simultaneously, the PPS fiber is discongested in the waterpower fluffer by 0.06% weight concentration make slurries (B).
Slurries (A), (B) are joined by amount of calculation join in the slurry still, in joining the slurry still, add 5 parts of polyethylene glycol oxides and 5 parts of aluminium-magnesium silicate thickeners simultaneously in water, increase the denseness of slurries simultaneously, the shaping of being convenient to manufacture paper with pulp so that fiber is uniformly dispersed.The shaping of manufacturing paper with pulp on general paper machine of slurries after will preparing then, drying is given in dehydration.Yield dried ground paper then and pass through from drying tunnel, drying tunnel temperature is controlled at and coheres the above 10-50 of fiber fusing point ℃, and further heat is bundled into type on the heat bundle machine that coheres the following 30-50 of fiber fusing point ℃ being lower than.Heat is pricked roll temperature and is controlled at 260-80 ℃; Heat is pricked the roller linear pressure and is controlled at about 1000N/cm.The density of resulting paper is 60-70g/m
2, tensile strength is greater than 3.5KM/m (MD), and LOI (%) is greater than 45.
Embodiment 2
In the present embodiment 2, the proportioning of Fanglun 1414/polyphenylene sulfide fibre composite paper is:
Fanglun 1414 (5-6mm) 60 weight portions
Polyphenylene sulfide fibre (3-6mm) 40 weight portions
Used polyphenylene sulfide fibre is with example 1.Used Fanglun 1414's method for making is: in the ratio of 1.0 moles of p-phenylenediamine (PPD) and 1.01 moles of paraphthaloyl chlorides, with above-mentioned reactant, at NMP/CaCl
2Carry out the low temperature solution polymerization reaction in the dicyandiamide solution and generate resin.Then resin dissolves is made lysotropic liquid crystal in the concentrated sulfuric acid, again through doing the pristine fibre that spray/wet spinning makes.Spinnerets 1000 holes, aperture 0.07mm spins 300 meters/minute of speed.Precursor carries out hot drawing-off under 350 ℃ of conditions under nitrogen protection, weak point is cut into the staple fibre that length is the 5-6 millimeter at last.In order to increase the compatibility of fragrant heterocycle fiber and polyphenylene sulfide fibre, need before the use Fanglun 1414 to be carried out surface treatment with coupling agent KH-550.
When producing composite sheet, respectively Fanglun 1414 and polyphenylene sulfide fibre are discongested in the waterpower fluffer by 0.06% weight concentration earlier and make slurries (A) and (B), and join respectively to join and starch in the still.Press embodiment 1 described method then and add surface-activity and thickener.The preparation method of composite sheet is identical with embodiment 1, and heat is pricked the roller linear pressure and is controlled at about 300N/cm.The density of resulting paper is 60-70g/m
2, tensile strength is 3.5KM/m (MD), LOI (%) is greater than 35.
Embodiment 3
In the present embodiment 3, the proportioning of Fanglun 1313/polyphenylene sulfide fibre composite paper is:
Fanglun 1313 (3-6mm) 80 weight portions
Polyphenylene sulfide fibre (3-6mm) 20 weight portions
Used polyphenylene sulfide fibre is with example 1.Used Fanglun 1313 is commercial product.In order to increase the compatibility of Fanglun 1313 and polyphenylene sulfide fibre, Fanglun 1313 need carry out surface treatment with KH-550.
When producing composite sheet, respectively Fanglun 1313 and polyphenylene sulfide fibre are discongested in the waterpower fluffer by 0.06% weight concentration earlier and make slurries (A) and (B), and join respectively to join and starch in the still.Press embodiment 1 described method then and add surface-activity and thickener.The preparation method of composite sheet is identical with embodiment 1, and heat is pricked the roller linear pressure and is controlled at about 2000N/cm.The density of resulting paper is 60-70g/m
2, tensile strength is 3.5KM/m (MD), LOI (%)=35.
Embodiment 4
In the present embodiment 4, the proportioning of Technora fiber/polyphenylene sulfide fibre composite paper is:
Technora fiber (3-6mm) 50 weight portions
Polyphenylene sulfide fibre (3-6mm) 50 weight portions
The Technora fiber that the present invention uses is the product of Japanese Supreme Being people company.Length is the staple fibre of 5-6 millimeter, fiber number 2.0D.The preparation method of composite sheet is identical with embodiment 1, and heat is pricked the roller linear pressure and is controlled at about 3000N/cm.The density of resulting paper is 60-70g/m
2, tensile strength 3.5KM/m (MD), LOI (%)=30
Embodiment 5
In the present embodiment 5, the proportioning of the high-performance of fragrant heterocycle aramid fiber/PET composite sheet is:
Aromatic heterocyclic modified aramid fiber 3-6mm) 70 weight portions
PET (polyethylene terephthalate) fiber (3-6mm)
30 weight portions
The preparation method of composite sheet is identical with embodiment 1.The density of resulting paper is 65-75g/m
2, LOI (%)=30, the elongation at break height (greater than 35%) of paper, production cost is low, is fit to do the H class F insulating material F and uses.
Embodiment 6
In the present embodiment 6, the proportioning of aromatic heterocyclic modified aramid fiber composite sheet is:
Aromatic heterocyclic modified aramid fiber 5-6mm) 70 weight portions
Polyphenylene sulfide fibre fiber (4-6mm) 25 weight portions
Expanded graphite 5 weight portions
The aromatic heterocyclic modified aramid fiber length that the present invention uses is the staple fibre of 5-6 millimeter, fiber number 1.5d.The polyphenylene sulfide fibre fibre length is the staple fibre of 4-6 millimeter, fiber number 1.5d.The preparation method of composite sheet is identical with embodiment 1.The density of resulting paper is 80-100g/m
2, LOI (%) is greater than 45, and resistivity is 0.1 Ω-cm
Embodiment 7
In the present embodiment 7, poly-between between phenyl-diformyl the proportioning of benzene two fibers/PET composite sheet be:
Benzene two fibers (3-6mm) 65 weight portions between phenyl-diformyl between poly-
Polybutylene terephthalate (PBT) fiberoptic fiber (3-6mm) 35 weight portions
The preparation method of composite sheet is identical with embodiment 1.The quantitative of resulting paper is 65g/m
2, LOI (%)=26
Embodiment 8
In the present embodiment 8, poly-between between phenyl-diformyl the proportioning of benzene two fibers/PA66 composite sheet be:
Benzene two fibers (3-6mm) 65 weight portions between phenyl-diformyl between poly-
PA66 fiber (3-6mm) 35 weight portions
The preparation method of composite sheet is identical with embodiment 1.The quantitative of resulting paper is 50g/m
2, LOI (%)=27.
Consisting of of Nomex benzimidazole fiber: 2-(4 aminophenyl)-5 (6) aminophenyl benzimidazoles, p-phenylenediamine (PPD), chloro p-phenylenediamine (PPD), paraphthaloyl chloride.
Consisting of of aramid III fiber: 2-(4 aminophenyl)-5 (6) aminophenyl benzimidazoles, p-phenylenediamine (PPD), paraphthaloyl chloride.
Consisting of of Technora fiber: 3,4 '-diaminodiphenyl ether, p-phenylenediamine (PPD), paraphthaloyl chloride.
The Fanglun 1414 consists of: p-phenylenediamine (PPD), paraphthaloyl chloride.
Consisting of of Fanglun 1313: m-phenylene diamine (MPD), m-phthaloyl chloride.
The method for making of the modification of aramid fiber that the present invention uses is: in 0.2 mole p-phenylenediamine (PPD), 0.4 mole chloro p-phenylenediamine (PPD), 0.4 mole 2-(4 aminophenyl)-5 (6) aminophenyl benzimidazoles and the ratio (mol ratio can be regulated as required) of 1.01 moles of paraphthaloyl chloride reactions, with above-mentioned reactant, at NMP/CaCl
2Carry out the low temperature solution polymerization reaction in the dicyandiamide solution and generate resin solution.Directly make pristine fibre by doing spray/wet spinning or wet spinning then with resin solution.Spinnerets 300 holes, aperture 0.08mm spins 20 meters/minute of speed.Precursor carries out hot drawing-off under 350 ℃ of conditions under nitrogen protection, weak point is cut into the staple fibre that length is the 3-6 millimeter at last.The performance indications of fiber are as follows:
| Tensile strength (Gpa) | 4.5-5.0 |
| Extension at break (%) | 3-4 |
| Tensile modulus (GPa) | 140-148 |
| Density (g/cm 3) | 1.34 |
| Fusing point (℃) | 500 |
| Moisture absorption ratio (%) (65%RH) | 3-4 |
| LOI(％) | 40-45 |
It should be noted that this resin solution is the good surface finishing agent of paper.Carry out surface-treated paper with this finishing agent and have higher insulating properties.
The Fanglun 1414 that the present invention uses: be to use p-phenylenediamine (PPD) and paraphthaloyl chloride at NMP/CaCl
2Carry out the low temperature solution polymerization reaction in the dicyandiamide solution and make resin, then resin dissolves is made liquid crystal solution in the concentrated sulfuric acid, again through doing the pristine fibre that spray/wet spinning makes.This fiber uses for making composite fibre paper after hot drawing-off, weak point are cut into the short fiber that length is the 2-8 millimeter.
Fanglun 1414's performance is as follows:
| Tensile strength (Gpa) | 2.8-3.2 |
| Extension at break (%) | 3-4.5 |
| Tensile modulus (Gpa) | 70-90 |
| Density (g/cm 3) | 1.45 |
| Fusing point (℃) | 550 |
| Moisture absorption ratio (%) (65%RH) | 4-5 |
| LOI(％) | 28 |
| Moisture absorption ratio (%) (65%RH) | 0.2-0.3 |
| LOI(％) | 45-60 |
The Fanglun 1313 that the present invention uses: be Nomex and the Teijinconex staple fibre that U.S. Du company of group and Japanese Supreme Being people company produce.Length 3-8mm, filament number 1-3.8D.Its chemical composition is the product of m-phenylene diamine (MPD) and m-phthaloyl chloride.
. the performance of Fanglun 1313 is as follows:
| Tensile strength (Gpa) | 0.55-0.66 |
| Extension at break (%) | 35-50 |
| Tensile modulus (Gpa) | 9-10 |
| Density (g/cm 3) | 1.37 |
| Decomposition temperature (℃) | 500 |
| Moisture absorption ratio (%) (65%RH) | 4-5 |
| LOI(％) | 28 |
| LOI(％) | 24-28 |
The polyphenylene sulfide fibre that the present invention uses is to be the linear polyphenylene sulfide resin of raw material production with vulcanized sodium and paracide; Make precursor with melt spinning method, precursor is through hot drawing-off, curling, the short staple fibre (length 2-8 millimeter) that obtains of cutting then.The performance indications of fiber are as follows:
| Tensile strength (Cn/dtex) | 0.5-0.6 |
| Extension at break (%) | 25-40 |
| Tensile modulus (Cn/dtex) | 55-65 |
| Density (g/cm 3) | 1.34 |
| Fusing point (℃) | 285 |
| Moisture absorption ratio (%) (65%RH) | 0.2-0.3 |
| LOI(％) | 40-45 |
The polyester fiber that the present invention uses is to be the staple fibre that Yizheng Fiber Optical plant factory produces.Length is the 5-6 millimeter, fiber number 1.5D.
The PA66 fiber that the present invention uses is to be the fiber that refreshing horse group produces.Through be cut into the 5-6 millimeter staple fibre use fiber number 1.5-2.0d.
Claims (5)
1. make the manufacture method that binder is produced aramid fiber paper with thermoplastic fibre for one kind, this fibrous paper contains:
Aramid fiber 50-80 weight portion
Thermoplasticity is cohered fiber 50--20 weight portion;
Behind the aramid fiber cutting short-forming fiber, discongest in the waterpower fluffer by 0.06% weight concentration and to make slurries (A), thermoplasticity is cohered fiber discongest in the waterpower fluffer by 0.06% weight concentration and make slurries (B); Slurries (A), (B) are joined by described weight portion join in the slurry still, adds the modulation of suitable conventional dispersant and thickener and obtain paper pulp,, dewater the shaping of on general paper machine, manufacturing paper with pulp of the paper pulp after preparing, predrying; Ground paper after predrying passes through from drying tunnel, and further on heat bundle machine heat be bundled into type and obtain finished paper; Drying tunnel temperature is controlled at thermoplasticity and coheres the above 10-50 of fiber fusing point ℃, and heat bundle roll temperature is controlled at and coheres the following 30-50 of fiber fusing point ℃; Heat is pricked the line pressure 500-3000cN/cm of roller.
According to claim 1 described make the manufacture method that binder is produced aramid fiber paper with thermoplastic fibre, it is characterized in that described aramid fiber comprises: Nomex benzimidazole fiber, aramid III fiber, poly-between benzene two fibers, Fanglun 1414, Technora fiber between phenyl-diformyl.
According to claim 1 described make the manufacture method that binder is produced aramid fiber paper with thermoplastic fibre, it is characterized in that described thermoplasticity is cohered fiber and comprised polyphenylene sulfide fibre fiber, polyester fiber, PA66 fiber.
According to claim 1 described make the manufacture method that binder is produced aramid fiber paper with thermoplastic fibre, it is characterized in that, in order to prevent that thermoplastic fibre from hot high pressure bundle process roll banding taking place, adopt earlier blank paper to be preheating in drying tunnel more than the softening point that coheres fiber, carry out hot high pressure below the softening point that coheres fiber and prick being lower than again.
According to claim 2 described make the manufacture method that binder is produced aramid fiber paper with thermoplastic fibre, it is characterized in that the consisting of of described Nomex benzimidazole fiber: 2-(4 aminophenyl)-5 (6) aminophenyl benzimidazoles, p-phenylenediamine (PPD), chloro p-phenylenediamine (PPD), paraphthaloyl chloride; Consisting of of aramid III fiber: 2-(4 aminophenyl)-5 (6) aminophenyl benzimidazoles, p-phenylenediamine (PPD), paraphthaloyl chloride; Consisting of of Technora fiber: 3,4 '-diaminodiphenyl ether, p-phenylenediamine (PPD), paraphthaloyl chloride; The Fanglun 1414 consists of: p-phenylenediamine (PPD), paraphthaloyl chloride; Consisting of of Fanglun 1313: m-phenylene diamine (MPD), m-phthaloyl chloride.
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| CNA2006100220825A CN101165269A (en) | 2006-10-20 | 2006-10-20 | Preparation method for producing aramid fiber paper by using thermoplastic fiber as adhesive |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106087529A (en) * | 2016-06-08 | 2016-11-09 | 华南理工大学 | The preparation method of self-reinforcing is pressed in a kind of high intensity aramid fiber paper and dissolving thereof again |
| CN111350098A (en) * | 2018-12-24 | 2020-06-30 | 上海钱丰纺织品有限公司 | Thermal stability paper material with excellent chemical corrosion resistance and preparation method thereof |
| CN111733598A (en) * | 2020-06-29 | 2020-10-02 | 江南大学 | Liner paper and preparation method thereof |
-
2006
- 2006-10-20 CN CNA2006100220825A patent/CN101165269A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106087529A (en) * | 2016-06-08 | 2016-11-09 | 华南理工大学 | The preparation method of self-reinforcing is pressed in a kind of high intensity aramid fiber paper and dissolving thereof again |
| CN106087529B (en) * | 2016-06-08 | 2018-06-22 | 华南理工大学 | The preparation method of self-reinforcing is pressed in a kind of high intensity aramid fiber paper and its dissolving again |
| CN111350098A (en) * | 2018-12-24 | 2020-06-30 | 上海钱丰纺织品有限公司 | Thermal stability paper material with excellent chemical corrosion resistance and preparation method thereof |
| CN111733598A (en) * | 2020-06-29 | 2020-10-02 | 江南大学 | Liner paper and preparation method thereof |
| CN111733598B (en) * | 2020-06-29 | 2021-11-02 | 江南大学 | Liner paper and preparation method thereof |
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