WO2018217182A2

WO2018217182A2 - Fiber produced from pan-pvc mixture

Info

Publication number: WO2018217182A2
Application number: PCT/TR2017/050599
Authority: WO
Inventors: Ilhan CANPOLAT
Original assignee: Aksa Akrilik Kimya Sanayii Anonim Sirketi
Priority date: 2016-11-28
Filing date: 2017-11-27
Publication date: 2018-11-29
Also published as: WO2018217182A4; WO2018217182A3

Abstract

The invention is related to a fire retardant fiber (1) which comprises polyacrylonitrile (PAN) (2), polyvinylchloride (PVC) (3), nano-sized additive (4), solvent (5), surfactant (6), tank 1 (7), tank 2 (8), heat exchanger (9), static mixer (10) and dynamic mixer (11) and surfactant – nano-sized additive (12).

Description

DESCRIPTION FIBER PRODUCED FROM PAN-PVC MIXTURE

TECHNICAL FIELD OF THE INVENTION

The invention is related to a fiber highly resistant to fire that is produced from a polyacrylonitrile (PAN) and polyvinyl chloride (PVC) mixture.

PRIOR ART

Acrylic fiber is a kind of synthetic fiber that is similar to wool, is used alone or by being blended with natural and/or synthetic fiber types and it has a wide range of application areas. Acrylic fiber that has properties such as being easily washable and keeping its shape, being resistance against moths, oil and chemicals, being paintable with bright colors at high purity, is used in various fields such as clothing, domestic and similar textile, synthetic hair, wigs, plush, buildings, defense and security.

Polyacrylonitrile (PAN) polymer is a material with a synthetic polymer structure similar to natural fibers such as wool and cotton, which is frequently used in textile applications such as clothing, home textile etc. and it is obtained by radical chain polymerization of acrylonitrile monomers

Polyvinylchloride (PVC) is a polymer material that does not bear similarities with fibers, it fire retardant due to its halogen content, highly resistant against UV (ultra violet) rays, and chemicals. Polyvinylchloride (PVC) is not commonly used in textile since it is not suitable for production of thread-textile and since it does not meet properties such as softness, being touchable, water absorption etc. which are basic properties for textile products.

Due to abovementioned reasons, both in order to utilize the properties of acrylic fiber in textile and to utilize the fire retarding properties of polyvinylchloride (PVC), poly (acrylonitrile-co-vinylchloride) fibers known as modacrylic fiber is developed which, in its composition, contains acrylonitrile between 35-85% and vinyl chloride as co- monomer besides acrylonitrile. Modacrylic polymer is produced by a mixture of vinylchloride (VCM) and acrylonitrile (AN) in the polymerization process. In the prior art modacrylic polymer is obtained by free radical polymerization through suspension, emulsion or solution methods. In the production process of modacrylic polymer, monomers are used. The monomer structures are harmful to health and the environment since they have carcinogenic effects, flammable and explosive properties. Since they are harmful to human health and to the environment, it is required to take additional precautions during the process thereof.

In the state of the art; modacrylic polymer is a high cost product due to the chemical reactions during its production process. As the process cost is high it causes the product to be rare on the market and for it to have a high sales price.

The patent applications CN1 03497453 (A) "PVC (polyvinyl chloride)/AAS (Acrylonitrile- Acrylicester-Styrene Copolymer) alloy reinforced sectional material" discloses a PVC (polyvinyl chloride)/AAS (Acrylnitril-Acrylicester-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.

In the document with application number TPE 2016/02588 FIBER PRODUCED FROM TERNARY POLYMER MIXTURE a fiber obtained from a co-polyacrylonitrile (co-PAN), polyvinylchloride (PVC) and co-polyvinylchloride (co-PVC) mixture is described. In said invention, the fiber is produced from a physical mixture of co-polyacrylonitrile (co- PAN), polyvinylchloride (PVC) and co-polyvinylchloride (co-PVC) polymers and there is no negative situation for human health and safety occurring during production since there is no need for chemical reactions and monomers during the production stage. However, since there are three different polymers, a solution preparation tank and process is required for mixing each one of the polymers. Besides, the cost of co- polyvinylchloride (co-PVC) is relatively more than the cost of homo-PVC. Therefore, the product obtained from double mixture (co-PAN + homo-PVC) will be relatively cheaper than the ternary mixture.

As a result, all of the abovementioned problems have made it necessary to bring a novelty to the related technical field.

BRIEF DESCRIPTION OF THE INVENTION

The present invention is related to a fiber produced from a polyvinyl chloride (PVC) and polyacrylonitrile (PAN) polymer mixture that meets all of the abovementioned requirements, that eliminates all disadvantages and that brings some additional advantages, the invention is related to the production of a fire retardant fiber by enabling the homogenous mixture of said two polymers which usually do not mix homogenously, by means of nano-sized additives.

OBJECTS OF THE INVENTION

The present invention requires to bring a technical novelty in the related field and to eliminate the abovementioned problems.

The present invention is related to a fiber produced from a polyvinyl chloride (PVC) and polyacrylonitrile (PAN) mixture that meets the abovementioned requirements, that eliminates all the disadvantages and that brings some additional advantages. The main object of the invention is to provide a novel fiber structure produced from a polyvinyl chloride (PVC) and polyacrylonitrile (PAN) mixture. Another object of the invention is to use nano-sized inorganic additives for homogenously mixing the polyvinyl chloride (PVC) and polyacrylonitrile (PAN) polymers.

Yet another object of the invention is to increase the homogeneity of the polymers via certain surfactants and compatibilizers.

As no monomers are used in the manufacturing process of mentioned mixture and the mentioned mixture obtained by a physical mixture of polymers with nano-sized inorganic additives the production process has no negative effect on the environment and human health.

Another object of the invention is to make the process less costly by producing a new fiber type through a two-step process without requiring the establishment of an additional plant via physical mixture of polyvinyl chloride (PVC) and polyacrylonitrile (PAN) polymers.

In the invention, since the raw material cost is reduced, accordingly the product cost is also reduced.

An object of the invention is to provide a fire retardant fiber, with UV resistance and chemical resistance via physical mixture of polyvinyl chloride (PVC) and polyacrylonitrile (PAN) polymers with nano-sized inorganic additivesadditive.

With this product, a high amount of oxygen required for the combustion reaction to take place.

Another object of the invention is to enable the product to exhibit a better result in parameters that affect the product quality such as paint and strength, since a fiber with a homogeneous structure is obtained by polyvinyl chloride (PVC) and polyacrylonitrile (PAN) mixture with nano-sized inorganic additives. In order to achieve all the above-mentioned objects that will be apparent from the detailed description provided below, the present invention is related to a fire retardant fiber that comprises polyacrylonitrile (PAN), polyvinylchloride (PVC), nano-sized inorganic additives. additive, solvents and surfactants.

BRIEF DESCRIPTION OF THE FIGURES Figure 1 shows the representative views of the components used in the production of the fiber (1 ) "a fire retardant fiber, produced from a polyvinyl chloride (PVC) and polyacrylonitrile (PAN) mixture" of the invention.

Figure 2 is the process steps of the production method of the fiber (1 ) "a fire retardant fiber, produced from a polyvinyl chloride (PVC) and polyacrylonitrile (PAN) mixture" of the invention.

Figure 3 shows the representative view of the polyvinyl chloride (PVC) and polyacrylonitrile (PAN) mixture structure.

Figure 4 shows the representative view of the mixture structure obtained by adding polyvinyl chloride (PVC), polyacrylonitrile (PAN) and surfactant.

Figure 5 shows the representative view of the mixture structure obtained by adding polyvinyl chloride (PVC), polyacrylonitrile (PAN) and co-polyvinyl chloride (co-PVC).

Figure 6 shows the representative view of the mixture structure obtained by adding polyvinyl chloride (PVC), polyacrylonitrile (PAN), co-polyvinyl chloride (co-PVC) and surfactant.

Figure 7 shows the representative view of the polyvinyl chloride (PVC), polyacrylonitrile (PAN) and nano-sized additive.

Figure 8 shows the representative view of mixture structure obtained by adding surfactant to the polyvinyl chloride (PVC), polyacrylonitrile (PAN) and nano-sized inorganic additives. additive. DESCRIPTIONS OF THE REFERENCE NUMBERS IN THE FIGURES

1. Fiber

2. Polyacrylonitrile (PAN)

3. Polyvinylchloride (PVC)

4. Nano-sized additive

5. Solvent

6. Surfactant

7. Tank 1

8. Tank 2

9. Heat exchanger

10. Static mixer

11. Dynamic mixer

12. Surfactant-nano-sized additive

DESCRIPTION OF THE PROCESS STEPS

The invention subject to the application titled "Fiber produced from PAN-PVC mixture" is enumerated as seen in the appended figures and the process steps corresponding to said numbers are described below. 101. Adding the solvent (5) to Tank 1 (7)

102. Adding the polyacrylonitrile (PAN) (2) to Tank 1 (7) and mixingthereof

103. Adding the surfactant - nano-sized additive mixture (12) to Tank 1 (7) and dissolving thereof

104. Passing the polyacrylonitrile (PAN) (2) and surfactant - nano-sized additive through the heat exchanger between 50-120°C to completely dissolve the mixture

105. Adding the solvent (5) to Tank 2 (8)

106. Adding the polyvinylchloride (PVC) (3) to Tank 1 (7) and mixing thereof

107. Passing the polyvinylchloride (PVC) (3) through the heat exchanger between 50-120°C to completely dissolve it, 108. Mixing the mixtures prepared in Tank 1 (7) and Tank 2 (8) by the help of the static mixer (1 0) or dynamic mixer (1 1 )

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

DETAILED DESCRIPTION OF THE INVENTION

In this detailed description, the "fiber obtained from PAN-PVC mixture" of the invention is described via non-limiting examples to provide a better understanding of the matter.

Additionally, some components or process steps prepared to provide a better understanding of the invention may be used in various forms in the sentences to provide content integrity. Components and process steps used in different expressions actually represent the related component or process step with the same number.

The invention is related to a fire retardant fiber (1 ) that is obtained from a polyvinyl chloride (PVC) (3) and polyacrylonitrile (PAN) (2) mixture. The fiber (1 ) which is the subject of the invention produced from polyvinyl chloride (PVC) (3) and polyacrylonitrile (PAN) (2) mixture comprises the elements of; polyacrylonitrile (PAN) (2), polyvinyl chloride (PVC) (3) polymers and nano-sized additives (4), solvent (5), surfactant (6), tank 1 (7), tank 2 (8), heat exchanger (9), static mixer (10), dynamic mixer (1 1 ) and surfactant - nano-sized additive (12).

Polyacrylonitrile (PAN) (2) is a type of thermoplastic polymer. Among the synthetic fibers, the fibers obtained from polyacrylonitrile (PAN) (2) are the ones that are much similar to wool and that are most commonly used among wool imitating products. Thus, it is a polymer based material that is most commonly used in textile fields such as clothing, home textile etc.

Polyvinylchloride (PVC) (3) is a type of thermoplastic polymer. It is resistant against acids and bases. Polyvinylchloride (PVC) (3) has high electrolysis property and it is resistant against fire due to its halogen content. It does not ignite when it contacts with open fire. It has great strength and resistance due to "K" value and grain size differences. The molecular weight of the polyvinylchloride (PVC) (3) is between 90.000 and 200.000. Its K value is between 44-1 1 0.

Polyacrylonitrile (PAN) (2) and polyvinylchloride (PVC) (3) are polymers that do not mix with each other due to their structures. Therefore, it is impossible to produce a homogeneous fiber (1 ) from a polyacrylonitrile (PAN) (2) and polyvinylchloride (PVC) (3) mixture.

In Figure 3, a representative view of polyacrylonitrile (PAN) and polyvinylchloride (PVC) mixture structure is shown. Polyvinyl chloride (PVC) (3) particles are not homogeneously dispersedin the polyacrylonitrile (PAN) (2). Polyvinyl chloride (PVC) (3) particles dimensionally have quite different radius from each other. Since fibers obtained from this mixture cannot be produced homogeneously, they cannot provide the desired results in parameters defining the product quality such as paint, burning and strength. The reason why polyacrylonitrile (PAN) (2) and polyvinylchloride (PVC) (3) do not mix into each other homogenously is that their surface tensions are different from each other. In order to enable homogenous mixing of polyacrylonitrile (PAN) (2) and polyvinylchloride (PVC) (3) with each other, the difference between their surface tensions must be reduced. In the invention, in order to reduce the surface tension difference between polyacrylonitrile (PAN) (2) and polyvinylchloride (PVC) (3), nano- sized additives (4) are used. The nano-sized additive (4) used in the invention is also used to increase fire resistance. Said nano-sized additive (4) is an inorganic material exhibiting synergic effect (in other words, an increase beyond the expected individual activities of separate elements, compound effect) with the halogens, having a particle size between 5 and 750 nanometers. As said nano-sized additive (4), antimonitroxide, zinc borate, aluminum hydroxide, aluminum trioxide, magnesium hydroxide, magnesium trioxide and similar materials are used.

Althoughthe fire-retardant effect of the antimontrioxide is very low when it use alone, it increases the fire resistance due to its synergic effect with halogens. It creates volatile compounds that increase the radical retaining effectiveness of the halogenated compounds. Thus, fire is prevented from advancing. Due to the chlorine atom in the structure of polyvinylchloride (PVC) (3), it is sufficient to use antimontrioxide alone to increase fire resistance. Aluminum Hydroxide (AI(OH)3) and Magnesium Hydroxide (Mg(OH)2) create water vapor by decomposing through endothermic reaction and at the same time the water vapor cools the polymer. During decomposition of AI(OH)3 and Mg(OH)2, a huge amount of heat is consumed and therefore ignition is retarded. Zinc borate detains and locks up the fumes by increasing cross bonding in polyvinyl chloride (PVC) (3).

As the solvent (5) is used as a dissolver, polar aprotic solvents such as DMAC, DMF, DMSO and similar solutions are used.

DBS, LAS etc., are used as said surfactant (6).

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

Tank 2 (8); is the place where the solvent (5) and polyvinylchloride (PVC) (3) are mixed, respectively.

The heat exchanger (9); is at 70-100°C temperature and it enables completely dissolving of mixtures mixed in tank 1 (7) and tank 2 (8).

The static mixer (1 0) and the dynamic mixer (1 1 ) are used to mix and homogenize the prepared PVC solution and PAN solution.

Surfactant - nano-sized additive (12) is a mixture comprising surfactant (6) and nano- sized additives (4). In said surfactant - nano-sized additive (1 2); the ratio of surfactant (6) is between 0.1 % and 2% and the ratio of nano-sized additive (4) is between 1 % and 10%.

In general, the invention is the production method of a fire retardant fiber (1 ), comprising the process steps of;

• Adding the solvent (5) into tank 1 (7) (1 01 ),

• Adding polyacrylonitrile (PAN) (2) into tank 1 (7) and mixing (102) thereof,

• Adding surfactant - nano-sized additive mixture (1 2) into tank 1 (7) and dissolving (103) thereof, • Passing the polyacrylonitrile (PAN) (2) and surfactant - nano-sized additive (12) through the heat exchanger between 50-120°C for complete dissolving (1 04) thereof,

• Adding the solvent (5) into tank 2 (8) (1 05),

• Adding polyvinylchloride (PVC) (3) into tank 2 (8) and mixing (106) thereof,

• Passing the polyvinylchloride (PVC) (3) through the heat exchanger between 50-120°C for complete dissolving (107) in the tank 2 (8),

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

• Obtaining the fiber (1 ) by wet spinning method from final mixture (109).

First, the solvent (5) is added into tank 1 (7). Following this, polyacrylonitrile (PAN) (2) is added into tank 1 (7) and mixed. Next, the surfactant - nano-sized additive (12) is added into tank 1 (7). The mixture (12) is passed through the heat exchanger (9) at 50- 120°C in order to completely dissolve the contents of said mixture.

Secondly, the solvent (5) is added into tank 2 (8). Then, the polyvinylchloride (PVC) (3) is added into tank 2 (8) and mixed. In Tank 2 (8), the polyvinylchloride (PVC) (3) is passed through the heat exchanger (9) at 50-1 20°C in order to completely dissolve the contents of said mixture.

Next, the mixtures prepared in tank 1 (7) and tank 2 (8) is mixed with the help of the static mixer (10) or the dynamic mixer (1 1 ).

In Figure 8, the representative view of the obtained mixture is shown. In said mixture, the polyvinylchloride (PVC) (3) is homogeneously dispersed in polyacrylonitrile (PAN) (2) and the radius of the polyvinylchloride (PVC) (3) particles are substantially decreased. Thus, the homogeneity of the fiber obtained from this mixture is maximized. Desired results are achieved at parameters defining the fiber quality such as paint, burning, strength etc.

In a preferred embodiment of the invention, instead of surfactant - nano-sized additive (12), only the nano-sized additive (4) is used. In Figure 7, the representative view of the mixture obtained by this way is shown. In another preferred embodiment of the invention, the surfactant - nano-sized additive (12) is added into Tank 2 (8) instead of Tank 1 (7) after the polyvinylchloride (PVC) (3) is dissolved in the solvent (5).

In the obtained mixture, the ratio of polyacrylonitrile (PAN) (2) is between 50% and 95%, the ratio of polyvinylchloride (PVC) (3) is between 5% and 50%, the ratio of nano-sized additive (4) is between 1 % and 10% and the ratio of the surfactant (6) is between 0.1 % and 2%.

By wet spinning method from the final mixture, a fiber (1 ) produced from polyacrylonitrile (PAN) (2) and polyvinylchloride (PVC) (3) mixture having high fire retardant properties is obtained.

In the wet spinning method; basically, the prepared polymer solution is fed into a bath containing water-solvent mixture after desired injections are performed, filtered and pressurized. The feeding is performed over a perforated plate that is called a spinneret which has micron-sized 10.000 to 1 00.000 holes on it. The polymer dissolved in the solvent solidifies and transforms into fiber filaments in the bath since it does not dissolve in water. This procedure is named coagulation and the bath in which the fiber filaments form is named a coagulation bath. To paint the fiber better in the next stage, the amount of solvent on it must be below 0.5%. Therefore, a washing operation is performed. In general, basic paints are used in painting the fibers. The acidic groups at the end of the polymer chain chemically bond with the basic paints and the fiber is painted. The painting operation is performed by penetration of paint into the fiber that has passed through the bath and from which the solvent is removed. In order to align (line up) the painted (or not painted) fiber filaments and to provide desired physical properties (dtex, elongation, strength) for the fiber, a fiber extrusion operation that is applied by heating in two separate baths is carried out. This procedure is called traction. After traction, the length of the fiber increases approximately by six-fold. The fibers washed, painted and elongated by traction are finished before drying. The finishing is a lubricant covering the fiber surface and it is a mixture of organic materials that is used to give the fiber the softness required for workability in textile operations and that is used to regulate the friction between the fiber and metal surfaces. The fiber exiting the finishing bath is dried by being passed through a series of drying drums heated by pressurized vapor. The water vapors leaving the fiber surface are removed in an aspiration system by being conveyed through air. The fiber filaments must be curly to hold on to each other, and not flat. The crimping procedure that provides the wool-like property and look to the fiber is implemented while the towing band is passed between two drums inside the crimping box. Another importance of the crimping operation is that it enables the vapor to thoroughly penetrate into fiber bands during annealing.

The LOI (Limit Oxygen Index) value of the fiber (1 ) produced from the pan-pvc mixture of the invention that is an indicator of fire resistance increases to the levels of 27-30%. Thus, the ignition reaction cannot occur in atmospheric conditions and in other conditions that do not enable the LOI value to reach %27-30 levels.

Claims

1 . The invention is a fire retardant fiber (1 ), characterized in that comprises polyacrylonitrile (PAN) (2), polyvinylchloride (PVC) (3), nano-sized additive (4), solvent (5) and surfactant (6).

2. The fiber (1 ) according to Claim 1 characterized in that it comprises 50% to 95%polyacrylonitrile (PAN) (2)

3. The fiber (1 ) according to Claim 1 characterized in that it comprises 5% to 50% polyvinylchloride (PVC) (3)

4. The fiber (1 ) according to Claim 1 characterized in that it comprises 1 % to 1 0% nano-sized additive

5. The fiber (1 ) according to Claim 1 or Claim 4 characterized in that said nano- sized additive (4) is an inorganic material such as antimonitroxide, zinc borate, aluminum hydroxide, aluminum trioxide, magnesium hydroxide, magnesium trioxide and the like, having particle (grain) size between 5 to 750 nanometers.

6. The fiber (1 ) according to Claim 1 characterized in that it comprises 0.1 % to 2%. surfactant (6).

7. The fiber (1 ) according to Claim 1 or Claim 6 characterized in that it comprises surfactant (6) such as DBS, LAS and the like.

8. The fiber (1 ) according to Claim 1 characterized by a LOI (Limit Oxygen Index) value which is an indicator of fire resistance to be at the range of 27-30%.

9. A method of producing fire retardant fiber (1 ) characterized in that it comprises the following process steps;

• Adding the solvent (5) into tank 1 (7) (1 01 ), Adding polyacrylonitrile (PAN) (2) into tank 1 (7) and mixing (102) thereof, Adding surfactant - nano-sized additive (12) into tank 1 (7) and dissolving (1 03) thereof,

Passing the polyacrylonitrile (PAN) (2) and surfactant - nano-sized additive (12) through the heat exchanger between 50-120°C for complete dissolving (1 04) thereof,

Adding the solvent (5) into tank 2 (8) (1 05),

Adding polyvinylchloride (PVC) (3) into tank 2 (8) and mixing (106),

Passing the polyvinylchloride (PVC) (3) through the heat exchanger between

50-120°C for complete dissolving (107) In tank 2 (8),

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

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