Thermoplastic acrylic resin and method for producing same, and resin composition

An acrylic resin and thermoplastic technology, applied in the direction of single-component synthetic polymer rayon, textiles and papermaking, fiber chemical characteristics, etc., can solve the problems of high solvent recovery cost and high drainage load

Pending Publication Date: 2020-11-03

KANEKA CORP

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AI-Extracted Technical Summary

Problems solved by technology

However, in the case of the wet spinning method, since the drainage load is high and the recovery c...

Method used

From the result of above-mentioned table 2, it can be seen that the thermoplastic acrylic resin of Examples 1-4 formed by graft copolymerization of macromolecular monomer and the acrylic resin of Comparative Examples 1-4 without macromonomer copolymerization Compared to that, the melt processing characteristics are improved. In addition, as can be seen from Table 1 above, the thermoplastic acrylic resins of Examples 1 to 4 obtained by graft-copolymerizing macromonomers and acrylic acid, which is a monomer capable of lowering the glass transition temperature of vinyl polymers, were positively The butyl ester has improved heat resistance compared with the acrylic resin of Comparative Example 3 in which acrylonitrile and vinyl chloride were copolymerized.

From the results of the above Table 3, it was confirmed that the thermoplastic acrylic resin composition (pellet shape) comprising the thermoplastic acrylic resin of Example 1 obtained by graft-copolymerizing the macromonomer was obtained by melt spinning Compared with the acrylic fiber of Example B1 using the acrylic resin of Comparative Example B2 or Comparative Example B3 that did not copolymerize the macromonomer, even in the state where the compounding amount of the plasticizer was reduced Melt spinning is also possible, and the apparent glass transition temperature is increased, so the heat resistance is improved.

From the results of the above Table 3, it was confirmed that the thermoplastic acrylic resins of Examples 2 and 3 were obtained by copolymerizing macromonomers containing 50% by mass or more of acrylate monomers having heteroatoms in the ester moiety. The melt viscosity of the thermoplastic acrylic resin composition (pellet form) and the thermoplastic acrylic resin of Example 1 obtained by copolymerizing a macromonomer made of a monomer whose ester moiety consists only of hydrocarbons Since the resin composition (pellet form) is comparatively low, it is excellent in melt processability.

In one or more embodiments of the present invention, the thermoplastic acrylic resin contains 35% by mass to 84.5% by mass of acrylonitrile, 15% by mass to 64.5% by mass of other ethylenically unsaturated mono monomers and 0.5 mass% to 40 mass% of polymers made of ethylenically unsaturated monomers. When the above-mentioned thermoplastic acrylic resin contains 35 mass % or more of acrylonitrile, heat resistance becomes favorable. The thermoplastic acrylic resin can improve the melt processability of the thermoplastic acrylic resin by including 0.5% by mass or more of a polymer composed of an...

Abstract

In at least one embodiment, the present invention relates to a thermoplastic acrylic resin which is a graft copolymer in which a stem polymer is an acrylic resin containing acrylonitrile and another ethylenically unsaturated monomer and a branch polymer is a polymer comprising an ethylenically unsaturated monomer, wherein acrylonitrile is contained in an amount of 35 to 84.5% by mass inclusive, the other ethylenically unsaturated monomer is contained in an amount of 15 to 64.5% by mass inclusive, and the polymer comprising an ethylenically unsaturated monomer is contained in an amount of 0.5 to 40% by mass inclusive. Provided are: a thermoplastic acrylic resin which is improved in melt processability without being deteriorated in heat resistance; a method for producing the thermoplastic acrylic resin; a thermoplastic acrylic resin composition; a molded article; an acrylic fiber; and a method for producing the acrylic fiber.

Application Domain

Monocomponent synthetic polymer artificial filament

Technology Topic

Polymer chemistryAcrylic fiber +5

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Examples

Experimental program(13)
Comparison scheme(13)

Example Embodiment

[0088] Example

[0089] The present invention is described below in more detail by way of examples. It should be noted that the present invention is not limited to the following examples.

[0090] First, various measurement methods and evaluation methods will be described.

[0091] (1) The mass-average molecular weight and number average molecular weight by gel permeation chromatography (manufactured by Tosoh Corporation "HLC-8320GPC") is calculated by GPC measurement method.

[0092] (2) an average particle diameter using a laser diffraction Horiba Seisakusho / scattering particle size distribution measuring cumulative volume of the volume fraction of particle size distribution measuring apparatus "Partica LA-950V2" in 50% by volume of particle diameter D50.

[0093] (3) a glass transition temperature of the acrylic resin is obtained by a value obtained by the following manner: using a differential scanning calorimeter "DSC-6100" SeikoInstruments Inc. manufactured from -80 ℃ at 20 ℃ / min warmed to after 160 ℃, again at 20 ℃ / min cooled to -80 ℃, once at 10 ℃ / minute from -80 ℃ to a value obtained when 160 ℃ thermal history after the exclusion.

[0094] (4) GPC-MALS was installed as a column in two TSKgel GMH manufactured by Tosoh "HLC-8220GPC" XL , A TSKgel G3000 XL , A TSKgel G2000 XL DMF, containing 50mM lithium bromide monohydrate as obtained eluent was measured. The degree of branching The degree of branching gM value (gM = mean square radius of gyration (mean radius of gyration of the branched polymer square / linear polymer)) is a mass average molecular weight 90,000, number-average molecular weight of 29,000 from acrylonitrile 50 mass% acrylic resin and 50% by mass of vinyl chloride polymer composition as a standard line, respectively, calculated from the average rotational radius calculated from the molecular weight distribution of the entire region.

[0095] (5) Melt processability is based on measuring microscope (VK-9500, KEYANCE Corporation, objective lens 10 times, 20 times the contents of the lens, the overall 200-fold) using Ultra-deep color 3D profile of the hot sample (resin plate) of the transmission light observation result, using the following judgment criteria.

[0096] Good: particle diameter of the powder 10μm or more was observed in 10 fields at 200-fold in the presence of only less than 50 points in total.

[0097] Poor: particle diameter of 10 fields of view observed at more than 200-fold powder of 10μm in total there are more than 50 points.

[0098] Not: kneading can not be suitably prepared by hot pressing the sample was observed.

[0099] (6) The melt viscosity is used Capilograph (Toyo Seiki Seisakusho, Ltd., Model "Capilograph 3B"), using a test speed of 10mm / min, the holes are 0.05cm, a cylinder radius 0.4775cm, a barrel temperature of 160 ℃, a hold time of 60 seconds, into 10g acrylic resin molded body (pellet), extruded from 120 seconds, 180 seconds, 240 seconds after the melt viscosity, they are obtained from the measurement average.

[0100] (7) The apparent glass transition temperature of the acrylic fiber refers to a peak temperature of tanδ. Tan [delta] peak temperature of dynamic viscoelasticity (tan [delta]) becomes maximum is dynamic viscoelasticity (tan [delta]) in accordance with JIS K 7244, using a fiber loss modulus values measured thermal analysis measuring apparatus (E ") and the storage modulus value (E '), calculated by the following formula.

[0101] Dynamic viscoelasticity (tanδ) = loss modulus (E ") / storage modulus (E ')

[0102] Thermal analysis measuring apparatus (manufactured by Seiko Instruments Inc., type "SSC / 5200"), at a vibration frequency of 0.05Hz, load of 25mN ± 10mN, at a heating rate of 5 ℃ / min condition, according to JIS K 7244, the fiber was measured loss modulus (E ") and the storage modulus (E '), was calculated by the following formula dynamic viscoelasticity (tanδ), dynamic viscoelasticity (tan [delta]) becomes maximum is a peak temperature of tan [delta] ( The apparent glass transition temperature).

[0103] (8) spinnability is evaluated in the following manner: measuring discharge from a number of holes 12 circular spinning nozzle, the nozzle 10 to 14 times the draft holes 12 can be performed without yarn breakage to have traction embodiment of the winding time, i.e. the time after the start of the winding yarn breakage to occur, with the embodiment 3 times the average value of the evaluation time (drawing time) and the product of drawing of the nozzle.

Example Embodiment

[0104] (Production Example 1)

[0105] Charged with CuBr 554g in separable flask equipped with a reflux tube and a stirrer 2L, the interior of the reaction vessel was purged with nitrogen. Next, acetonitrile was added 73.8mL, the separable flask was placed in an oil bath at 70 deg.] C, the contents were stirred for 30 minutes. Then, 132g of n-butyl acrylate in the separable flask, methyl 2-bromopropionate 7.2 mL, pentamethyl diethylene triamine 4.69mL, to initiate the reaction. It was heated with stirring at 70 ℃, while continuously added dropwise over 90 minutes n-butyl acrylate (528g), stirred for 80 minutes and further heated at 70 ℃. The reaction mixture was diluted with toluene and through an activated alumina column, by distilling off the volatile components under reduced pressure, to thereby obtain a Br group at one terminal of poly (n-butyl acrylate).

[0106] 800mL of methanol was charged in the flask was cooled to 0 ℃. Fractional To this was added the potassium t-butoxide (130g). Next, the flask was kept at 0 deg.] C, was added dropwise acrylic acid (100g) in methanol (concentration of 0.5g / mL) 200mL. Then, the temperature of the reaction solution was returned to room temperature, the volatile component was distilled off by reduced pressure from the reaction solution is 0 deg.] C, thereby obtaining a potassium acrylate (CH 2 = CHCO 2 K).

[0107] In 500mL flask was charged with a reflux tube obtained in the above-described one end Br poly (n-butyl acrylate) 150g, potassium acrylate 7.45g, dimethylacetamide 150mL, heated and stirred for 3 hours at 70 ℃. Then, a reaction mixture of dimethylacetamide was distilled off from the reaction mixture was dissolved in toluene, after passing through an activated alumina column, toluene was distilled off, thereby obtaining an acryloyl group at one terminal of poly (n-butyl acrylate) macromer. The resulting acryloyl group at one terminal of poly (n-butyl acrylate) macromonomer number average molecular weight of 12,000, a molecular weight distribution (weight average molecular weight / number average molecular weight) was 1.1.

Example Embodiment

[0108] (Production Example 2)

[0109] Except acrylate, 2-methoxyethyl acrylate, n-butyl acrylate in place of 2-bromo methyl propionate feed rate was changed to 14.4 mL, and the same manner as in Production Example 1 to obtain a single terminal acryloyl poly (acrylate, 2-methoxyethyl acrylate). The resulting acryloyl group at one terminal of poly (acrylate, 2-methoxyethyl acrylate) macromonomer number average molecular weight of 6000, a molecular weight distribution (weight average molecular weight / number average molecular weight) was 1.24.

PUM

Property	Measurement	Unit
The average particle size	169.5	µm
Glass transition temperature	85.6	°C
The average particle size	143.4	µm

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