WO2017151078A1

WO2017151078A1 - Fiber produced from ternary polymer mixture

Info

Publication number: WO2017151078A1
Application number: PCT/TR2017/050046
Authority: WO
Inventors: Ahmet SAFA ISIK; Gürcan KOMAN; Deniz DEMIRCI; Emrah EREN; Canan TUTUNCU; Ilhan CANPOLAT; Orhan Caliskan
Original assignee: Aksa Akrilik Kimya Sanayii Anonim Sirketi
Priority date: 2016-02-29
Filing date: 2017-01-31
Publication date: 2017-09-08
Also published as: JP2019507253A; KR20180114906A; EP3423615A1; CN108699730A

Abstract

The invention, relates to a fiber produced from ternary polymer mixture, developed for use generally in clothing, home and similar textiles, synthetic hair, wigs, plush, construction, defense and in the protective clothes, having quality and high fire-resistance. Fiber (1) comprises Co-Polyacrylonitrile (co-PAN) (2), Polyvinylchloride (PVC) (3), and Co-Polyvinylchloride (co-PVC) (4).

Description

FIBER PRODUCED FROM TERNARY POLYMER MIXTURE

FIELD OF INVENTION

Current Invention relates to fiber produced physically from ternary polymer mixture of Co-polyacrylonitrile (co-PAN), Polyvinyl chloride (PVC) and Co-polyvinyl chloride (co- PVC), which is suitable for yarn-fabric manufacturing process and resistant to fire has been developed for use generally in clothing, home and similar textiles, synthetic hair, wigs, plush, construction, defense and in the security field.

STATE OF ART

Acrylic fiber is a type of synthetic fiber which is similar to wool. In addition, it is a textile raw material used alone or mixed with other natural and/or synthetic fiber types such as cotton, wool, polyester, nylon. It has a wide range of usage, ranging from carpet to upholstery, yarn to hand-knitting, velvet to socks and canvas.

Acrylic fiber is an ideal fiber for the yarn production process and the textile process. On the other hand, Polyvinylchloride (PVC) is a product that is not much used in the textile sector and has limited use as fibers. PVC is not widely used in textiles because both it is not suitable for yarn-fabric production and it can't meet some basic properties (softness, touching, water retention etc.) required for textile. However, the polyvinylchloride (PVC) polymer is resistant to fire due to its halogen group content. Due to the reasons mentioned above, poly (acrylonitrile-co-vinyl chloride) fibers, known as modacrylic fibers have been developed both to utilize the properties that acrylic fibers have brought to textile and as well as to benefit from the fire resistance property of polyvinylchloride (PVC) polymer. Modacrylic polymer is produced from the mixture of vinyl chloride (VCM) and acrylonitrile (AN) monomers at polymerization stage. Modacrylic is used in the textile industry essentially protective clothing, upholstery, plush, synthetic hair, wig sectors.

l Acrylonitrile (AN) is monomer of Polyacrylonitrile (PAN). Polyvinylchloride (PVC) is called as vinyl chloride (VCM) at monomer state, Modacrylic obtained from a mixture of acrylonitrile (AN) and vinyl chloride (VCM) monomers is produced as a result of a chemical polymerization reaction.

Co-Polyacrylonitrile (co-PAN) is an acrylic material that is frequently used in clothing, home and similar textile fields, and is a synthetic polymer-based material that resembles natural fibers such as wool and cotton. Polyvinyl Chloride (PVC) is a polymer material that doesn't have reasonable fiber properties but it has high fire resistance, UV (ultra violet) and high chemical resistance.

In the present state of art; Modacrylic polymer is obtained by free radical polymerization, suspension, emulsion or solution polymerization. Modacrylic production is disadvantageous in terms of safety precautions. Monomers are used in modacrylic production process. The products contain carcinogenic, flammable and explosive properties in monomeric form. This is also harmful to health and the environment. As the process is harmful to human health and environment; additional safety precautions should be taken.

In the present state of art; due to the chemical reaction in its production process Modacrylic is rare in the market and is at high cost products. This leads to increased cost and higher priced products in sales process for the end user.

In another known state of the art, there is a patent application titled "METHOD OF MANUFACTURING OXYGEN ABSORPTIVE RESIN COMPOSITION AND OXYGEN ABSORPTIVE RESIN COMPOSITION "under reference no JP2010179643 which is related to a fiber material developed for use in the textile field. The summary of this application is as follows: "Providing a method for the manufacturing of an oxygen absorbing resin composition having superior oxygen absorbing function (high oxygen absorption and high oxygen absorption rate) and superior machinabiiity as a problem to be solved, without creating an unpleasant odor for oxygen absorption. The solution comprising; The method of manufacturing an oxygen absorptive resin composition using a biaxial extruder includes a process to melt and knead a resin raw material inside the extruder. The resin raw material contains a thermoplastic resin (A) with a carbon-carbon double bond and at least, one kind of gas barrier resin (D) selected from the group consisting of a polyvinyl chloride-based resin, a polyacrylonitrile- based resin and a polyvinyl alcohol-based resin. The extruder is equipped with two or more feed openings and a vent port located downstream from the feed opening. The resin raw material is supplied from a first feed opening located at the extreme end of the upstream side of the extruder, and water is supplied from a second feed opening downstream from the first feed opening and removed from the vent port. "

When the patent document mentioned above is examined, it is understood that there are differences with our invention and do not resemble each other. In the above- mentioned patent application, different polymer structures are used and the process proceeds with chemical reactions. In another known state of art, there is a patent application titled "PVC (polyvinyl chloride) / AAS (Aery Ion itrile-Acry lie acid-Styrene Copolymer) alloy reinforced sectional material" under reference number CN103497453 (A), which is developed to produce fiber type materials for use in the field of textiles. The summary of this application is as follows: "The invention discloses a PVC (polyvinyl chloride)/AAS (Acrylonitrile-Acrylic ester-Styrene Copolymer) alloy reinforced sectional material. The reinforced sectional material comprises, by weight, 100 parts of polyvinyl chloride sectional mixtures, 10-20 parts of polyacrylonitrile-butyl acrylate-styrene, 1-5 parts of chlorinated polyethylene and 1-5 parts of polyethylene wax. A process for manufacturing the PVC/AAS alloy reinforced sectional material includes the steps of manufacturing the polyvinyl chloride sectional mixtures; manufacturing the PVC/AAS alloy reinforced sectional material; mixing the mixtures with the material; squeezing the sectional material. The PVC/AAS alloy reinforced sectional material has the advantages that the concept is novel, the process is standard, the PVC/AAS alloy reinforced sectional material can be operated easily and conveniently and is high in cost performance; the PVC/AAS alloy reinforced sectional material is high in tensile strength, impact strength and toughness as compared with existing PVC sectional standard samples, and market requirements can be met effectively; the PVC/ASS alloy reinforced sectional material can be industrially manufactured on a large scale and can be widely applied to the field of processing for plastic materials. Our invention is not alike the afore-mentioned patent file. In addition, the polymer structures and production processes are different.

As a result, due to the above-mentioned problems and the inadequacy of the existing solutions, it has become necessary to develop fibers produced from the ternary polymer mixture.

BRIEF DESCRIPTION OF THE INVENTION The present invention is related to the fiber produced from ternary polymer mixture that meets the above-mentioned requirements, eliminates all disadvantages and provides some additional advantages.

The invention generally relates to fiber product produced from mixture of co- polyacrylonitrile (co-PAN), polyvinylchloride (PVC) and co-polyvinylchloride (co-PVC). There is no known product at home or abroad, obtained from ternary polymer mixture (co-PAN, PVC and co-PVC) or binary mixture (PVC + PAN or co-PVC + PAN).

The primary objective of the invention; is to produce new fiber types through physical mixing of co-polyacrylonitrile (co-PAN), polyvinylchloride (PVC) and co- polyvinylchloride (co-PVC) polymers. As no monomers are used in the manufacturing process of mentioned ternary mixture and the polymers are obtained only by the physical mixture, the production process does not pose any risk to the environment or human health.

One of the objectives of the invention; is to make the process less costly by producing new fiber types through physical mixing of co-polyacrylonitrile (co-PAN), polyvinylchloride (PVC) and co-polyvinylchloride (co-PVC) polymers. As the cost of production process will decrease, the product cost will also decrease.

Another objective of the invention; is to introduce a product with high UV and chemical resistance through physical mixing of co-polyacrylonitrile (co-PAN), polyvinylchloride (PVC) and co-polyvinylchloride (co-PVC). Amount of oxygen required to react with this product for fire reaction to take place is higher that creates fire resistant fiber.

The structural and characteristic features of the invention and all the advantages thereof will be understood more clearly by the following figures and the detailed explanations made by referring to these figures and for this reason the evaluation should be done taking these figures and detailed explanation into consideration.

BRIEF DESCRIPTION OF THE FIGURES Fiber produced from ternary polymer mixture; which is subject to our present application; is illustrated in the attached figures, in which:

Figure 1 is the representative view of elements used in fiber (1 ) production related to "Fiber produced from ternary polymer mixture" subject to the invention.

Figure 2 is the representative view of fiber (1 ) structure related to "Fiber produced from ternary polymer mixture" subject to the invention.

Figure 3 is a diagram, presenting the process steps of the fiber (1 ) production method related to "Fiber produced from ternary polymer mixture" subject to the invention.

"The drawings do not necessarily have to be scaled and the details, which are not necessary in order to understand the present invention, may have been excluded. Furthermore, at least substantially equal elements or elements with at least substantially equal functions are shown with the same numbers. " REFERENCE NUMBER

The invention entitled as "Fiber produced from ternary polymer mixture" which is the subject to this application, is numbered as shown in the attached figures, and the corresponding part names are given below;

1. Fiber

2. Co-Polyacrylonitrile (co-PAN)

3. Polyvinylchloride (PVC)

4. Co-Polyvinylchloride (co-PVC)

5. Solvent

6. Surfactant

7. Tank 1

8. Tank 2

9. Heat exchanger

10. Static mixer

11. Dynamic mixer

DISCLOSURE OF PROCESS STEPS The invention entitled as "Fiber produced from ternary polymer mixture" which is the subject to this application, is numbered as shown in the attached figures, and the corresponding process steps for these numbers are given below.

101. Adding solvent (5) to tank 1 (7)

102. Adding co-polyacrylonitrile (co-PAN) (2) to tank 1 (7) and mixing

103. Passing Co-Polyacrylonitrile (co-PAN) (2) through exchangers between70- 100°C for complete dissolution

104. Adding solvent (5) to tank 2 (8)

105. Adding surfactant (6) to tank 2 (8) and dissolution

106. Adding polyvinylchloride (PVC) (3) and co-polyvinylchloride (co-PVC)(4) to Tank 2 (8) and mixing 107. Passing polyvinylchloride (PVC) (3) and co-polyvinylchloride (co-PVC) (4) through exchangers between 70-100°C for complete dissolution in Tank 2 (8)

108. Mixing the mixtures prepared in tank 1 (7) and tank 2 (8) by means of static mixer (10) or dynamic mixer (1 1 )

109. Obtaining fibers (1 ) by wet spinning method from final mixture

DETAILED DESCRIPTION OF THE INVENTION

In this detailed description, the subject of invention "Fiber produced from ternary polymer mixture" is disclosed only for the better understanding of the subject and should not be considered as limiting to the scope of the invention.

In addition, some elements or process steps prepared to provide a better understanding of the invention may have been used in various ways to provide meaningful completeness within sentences. The elements or process steps used in different expressions actually represent the same numbered pertinent element or process step.

Fiber (1 ) produced from ternary polymer mixture; which is subject to invention, comprises the elements of: Co-polyacrylonitrile (co-PAN) (2), Polyvinylchloride (PVC) (3) and co-polyvinylchloride (co-PVC) (4) polymers, Solvent (5), surfactant (6), tank 1 (7), tank 2 (8), heat exchanger 9, static mixer (10) and dynamic mixer (1 1 ).

Sodium dodecyl benzenesulfonate, linear alkyl benzene sulfonate (LAS) etc. are type of mentioned surfactants (6) and polar aprotic solvents such as DMAC, DMF, DMSO and similar solutions are used as solvent (5)

Co-Polyacrylonitrile (co-PAN) (2) is an acrylic material, frequently used in textile fields like clothing, home textiles etc. Co-Polyacrylonitrile (co-PAN) (2) is a type of thermoset polymer. Co-Polyacrylonitrile (co-PAN) (2); contains 4-12% comonomer. This comonomer is Vinyl acetate or methyl acrylate. The molecular weight of Co- Polyacrylonitrile (co-PAN) (2) is between 90,000 and 200,000. Polyvinyl Chloride (PVC) (3) is a polymer material that doesn't have too much similar properties to fiber (1 ) but has high fire resistance, UV (ultra violet) and high chemical resistance. Polyvinyl Chloride (PVC) (3) is a type of thermoplastic polymer, classified as homopolymer and does not contain comonomer. The molecular weight of polyvinyl chloride (PVC) (3) is between 90,000 and 200,000. The K value is between 44 and 1 10.

Co-polyvinylchloride (co-PVC) (4) contains 4-20% comonomer. This comonomer is Vinyl acetate or methyl acrylate. Co-Polyvinylchloride (co-PVC) (4) molecular weight is between 90,000 and 200,000. The K value is between 44 and 1 10.

Tank 1 (7); is the place where the solvent (5) and the co-polyacrylonitrile (co-PAN) (2) are mixed, respectively.

Tank 2 (8) is the place where solvent (5), the surfactant (6), the polyvinylchloride (PVC) (3) and the co-polyvinylchloride (co-PVC) (4) are mixed respectively.

Heat exchanger (9) ensures complete dissolution of the mixtures which are mixed in the tank 1 (7) and the tank2 (8) at 70-100C. Static mixer (10); is used for mixing the prepared PVC / co-PVC solution with the co- PAN solution, the dynamic mixer (1 1 ); is used to mix and homogenize the co-PAN solution with the prepared PVC / co-PVC solution.

The subject of the invention is a new fiber produced from mixture of co- polyacrylonitrile (co-PAN) (2), polyvinylchloride (PVC) (3) and co-polyvinylchloride (co-PVC) (4), is used both in textile areas as acrylic fiber and fire-resistance technical fiber.

The amount of LOI (Limit Oxygen Index) which is the indication of the fire-resistance of the fiber increases to %25 to %40 level. Thus, under atmospheric conditions, and under conditions that does not allow the LOI values to reach to 25-40% levels, fire reaction does not occur. Co-Polyacrylonitrile (co-PAN) (2) and polyvinylchloride (PVC) (3) are products that are immiscible due to their nature. For this reason, it is impossible to produce homogeneous fiber (1 ) from a mixture of co-polyacrylonitrile (co-PAN) (2) and polyvinylchloride (PVC) (3). Also co-polyacrylonitrile (co-PAN) (2) and co- polyvinylchloride (co-PVC) (4) products are immiscible due to their structure. For this reason, it is impossible to produce homogeneous fiber (1 ) from co-polyacrylonitrile (co-PAN) (2) and co-polyvinylchloride (co-PVC) (4) mixture.

Three-dimensional gyroid structure is obtained by mixture of co-polyacrylonitrile (co- PAN) (2), polyvinyl chloride (PVC) (3) and co-polyvinylchloride (co-PVC) (4) polymers.

The proportions of polyvinylchloride (PVC) (3) and co-polyvinylchloride (co-PVC) (4) must be similar in order to obtain a three-dimensional gyroid structure. In the three- dimensional gyroid structure, the proportion of polyvinylchloride (PVC) (3) is between 5% and 25%. Likewise, the proportion of co-polyvinylchloride (co-PVC) (4) is between 5% and 25%. The ratio of co-polyacrylonitrile (co-PAN) (2) is between 50% and 90% for the purpose of coating the outer portion of the fiber (1 ). Wet fiber spinning method; is basically obtained by passing the dissolved polymer through spinneret in a suitable solvent (solvent (5)) and plasticizing it. This solution is sent to spinneret (perforated spraying head) in the coagulation (solidification) bath by means of a pump under constant pressure. Since the polymer mixture emerges from spinneret to a wet bath as a filament, thus coagulates, solidifies and forms the fibers (1 )

Production method of the fiber (1 ) subject to the invention:

First, solvent (5) is added to tank 1 (7). Then, co-polyacrylonitrile (co-PAN) (2) is added to tank 1 (7) and mixed. For complete dissolution of Co-Polyacrylonitrile (co- PAN) (2) It is passed through heat exchangers at temperatures between 70-100°C. Secondly, the solvent (5) is added to the tank 2 (8). Surfactant (6) is added to tank 2 (8) and dissolved. Polyvinylchloride (PVC) (3) and co-polyvinylchloride (co-PVC) (4) are then added into the tank 2 (8) and mixed. For complete dissolution of polyvinylchloride (PVC) (3) and co-polyvinylchloride (co-PVC) (4) in tank 2 (8) they are passed through heat exchangers at temperatures between 70-100C. Mixtures prepared in tank 1 (7) and tank 2 (8) are then mixed by means of static mixer (10) or dynamic mixer (1 1 ). The fiber (1 ) is obtained from the final mixture by the wet spinning method.

Claims

1. Invention is a fiber (1 ) produced physically from TERNARY polymer mixture which has been developed for use generally in clothing, home and similar textiles, Synthetic hair, wigs, construction, defense and in the protective field characterized in comprising the following: co-polyacrylonitrile (co-PAN) (2), polyvinylchloride (PVC) (3) and co-polyvinylchloride (co-PVC) (4) polymers, solvents (5) (DMAC, DMF, DMSO) and surfactant (6).

2. The fiber (1 ) according to claim 1 , characterized in comprising a tank 1 (7) in which the solvent (5) and the co-polyacrylonitrile (co-PAN) (2) are mixed, respectively.

3. The fiber (1 ) according to claim 1 , characterized in comprising a tank 2 (8) in which solvent (5), the surfactant (6), the polyvinylchloride (PVC) (3) and the co- polyvinylchloride (4) are mixed respectively.

4. The fiber (1 ) according to claim 1 , characterized in comprising a heat exchanger (9) which ensures complete dissolution of the mixtures which are mixed in the tank 1 (7) and the tank 2 (8) at 70-100C

5. The fiber (1 ) according to claim 1 , characterized in comprising a static mixer (10) which eventually allows all the mixtures to mix.

6. The fiber (1 ) according to claim 1 , characterized in comprising a dynamic mixer (1 1 ) which eventually allows all the mixtures to mix

7. The fiber (1 ) according to claim 1 , characterized in that LOI (Limit Oxygen Index) amount, which is indicator of fire resistance is in the range of 30-40%

8. The fiber (1 ) according to claim 1 , characterized in comprising co-polyacrylonitrile (co-PAN) (2) which is a type of thermosetting polymer.

9. The fiber (1 ) according to claim 1 , characterized in that, the said co- polyacrylonitrile (co-PAN) (2) contains 4 to 12% comonomer.

10. The fiber (1 ) according to claim 1 , characterized in comprising 60% to 90% co- polyacrylonitrile (co-PAN) (2) for the purpose of outer portion coating

11. The fiber (1 ) according to claim 1 , characterized in comprising polyvinylchloride (PVC) (3) which has a very high fire resistance, UV (ultra violet) and high chemical resistance.

12. The fiber (1 ) according to claim 1 , characterized in comprising polyvinylchloride (PVC) (3) which is a type of thermoplastic polymer.

13. The fiber (1 ) according to claim 1 , characterized in comprising 5% to 20% polyvinylchloride (PVC) (3).

14. The fiber (1 ) according to claim 1 , characterized in that the said co Polyvinylchloride (co-PVC) (4) contains from 4 to 20% comonomer.

15. The fiber (1 ) according to claim 1 , characterized in comprising 5% to 20% co- polyvinylchloride (co-PVC) (4).

16. The fiber (1 ) according to claim 1 , claim 9 or claim 12, characterized in that said comonomer is vinyl acetate or methyl acrylate.

17. The fiber (1 ) according to claim 1 , characterized in that; the mixture of said co- polyacrylonitrile (co-PAN) (2), polyvinylchloride (PVC) (3) and co-polyvinylchloride (co-PVC) (4) polymers is in a three-dimensional gyroid structure.

18. A method of producing fiber (1 ) which is generally developed for use in clothing, home and similar textile, construction, defense and protection areas;

Characterised that; Adding solvent (5) to tank 1 (7) (101 ),

Adding co-polyacrylonitrile (co-PAN) (2) to tank 1 (7) and mixing (102),

Passing co-polyacrylonitrile (co-PAN) (2) through exchangers between 70-100C for complete dissolution (103) ,

Adding solvent (5) to tank 2 (8) (104),

Adding surfactant (6) to tank 2 (8) and dissolution (105),

Adding polyvinylchloride (PVC) (3) and co-polyvinylchloride (co-PVC)(4) to tank 2 (8) and mixing (106),

Passing polyvinylchloride (PVC) (3) and co-polyvinylchloride (co-PVC) (4) through exchangers between 70-100°C for complete dissolution in tank 2 (8) (107), Mixing the mixtures prepared in tank 1 (7) and tank 2 (8) by means of static mixer (10) or dynamic mixer (1 1 ) (108)

And obtaining fibers (1 ) by wet spinning method from final mixture (109)