JPH0645661B2 - Vinyl chloride-allylamine copolymer - Google Patents

Description

TECHNICAL FIELD The present invention relates to a vinyl chloride-based copolymer, particularly a vinyl chloride-allylamine-based copolymer, which is excellent in hydrophilicity, water absorption and antistatic properties.

(Prior Art) Vinyl chloride-based copolymers are widely used as various molded products, sheets and films because they are inexpensive, have good moldability, and have excellent properties. However, vinyl chloride copolymers have poor wettability with water and lack hydrophilicity or water absorption. Moreover, this copolymer is very easily charged with electricity, which causes various obstacles such as electromagnetic interference. In order to prevent such electrification, it has been attempted to impart conductivity to the vinyl chloride copolymer.

As the vinyl chloride-based copolymer having conductivity, there are a copolymer prepared by blending a surfactant, carbon black, metal powder, conductive fibers and the like, and a copolymer coated with a surfactant on the surface. However, since the surfactant easily bleeds and falls off the surface of the molded body, the antistatic effect is not maintained. Although the antistatic effect is maintained by adding carbon black, metal powder, conductive fibers, etc., it is necessary to add a large amount of these conductive substances in order to obtain the desired conductivity. Therefore, it becomes expensive. A vinyl chloride-based copolymer having a noble metal or metal oxide adhered to its surface by vapor deposition, sputtering, etc., has an excellent antistatic effect, but is expensive and has low productivity.

In order to solve these drawbacks, carbon black,
There is a vinyl chloride-based copolymer in which a conductive coating material in which a conductive material such as metal powder is dispersed is used and which is coated on the surface. Although this copolymer is inexpensive and exhibits an excellent antistatic effect, the conductive material is different from the resin, and therefore bleeding and dropping may occur.

(Problems to be Solved by the Invention) The present invention is intended to solve the above-mentioned conventional problems, and an object thereof is to provide vinyl chloride-excellent in antistatic properties.
An object is to provide an allylamine-based copolymer. Another object of the present invention is to provide a vinyl chloride-allylamine copolymer excellent in hydrophilicity or water absorption. Still another object of the present invention is to provide a highly reactive vinyl chloride-allylamine copolymer.

(Means for Solving Problems) In the present invention, by introducing allylamine or a salt thereof as a copolymer unit of a vinyl chloride-based copolymer,
The conductivity of the copolymer is high; thereby, a vinyl chloride-based copolymer having excellent antistatic properties can be obtained; Moreover, since this copolymer has an amino group, it is excellent in hydrophilicity or water absorption In addition, it was completed based on the inventor's knowledge that the reactivity is also high.

The vinyl chloride-allylamine-based copolymer of the present invention is represented by the following formula, whereby the above object is achieved.

Where m and n are integers greater than or equal to 1 and R
Is an amino group and / or a Lewis acid salt of an amino group.

It is known that allylamine or its salt can be copolymerized with vinylpyrrolidone, dimethylaminoethylmethacrylate, β-methacryloyloxyethyltrimethylammonium chloride, acrylamide, acrylonitrile, hydroxyethyl acrylate, methylmethacrylate, vinyl acetate and styrene. (JP-A-61-2
(Disclosed in 03110 publication). However, it has not been confirmed that this allylamine or its salt copolymerizes with vinyl chloride. Therefore, in the present invention, an attempt was made to copolymerize allylamine or a salt thereof with vinyl chloride. As a result, a vinyl chloride-allylamine-based copolymer was obtained, and it was found that this copolymer was excellent in hydrophilicity, water absorption and conductivity. This vinyl chloride-allylamine-based copolymer was identified by elemental analysis (quantifying the weight of N atoms in the allylamine unit). Furthermore, according to the IR analysis of the copolymer, it was 2200
There is a NH ₃ ⁺ a wide range of absorption in ~3000cm ^-1, and 1650cm ^-1
Absorption of NH bending vibration was observed.

Examples of the amino acid Lewis acid salt represented by R in the above formula include hydrochloride, sulfate, sulfite, phosphate, phosphite, hypophosphite, nitrate and nitrite. Also, m
And n have, for example, the following relationship.

When n is in this range, the larger the value, the more hydrophilic or water-absorbing the vinyl chloride-based copolymer and the higher the conductivity. Therefore, the antistatic property of the copolymer becomes good. However, when the value of n exceeds the above range, the antistatic property of the copolymer is improved, but the shape stability is impaired. Therefore, such a copolymer cannot be used. Regarding the lower limit of the amount of allylamine or its salt present in the copolymer, the copolymer contains 3% by mole, more preferably 5% by mole or more of allylamine or its salt as a copolymerization component. However, it is desirable for imparting hydrophilicity, water absorption, antistatic properties, etc. to the copolymer.

The molecular weight of this copolymer is usually in the range of 800 to 300,000. Outside this range, processing of the copolymer becomes difficult.

The vinyl chloride-allylamine copolymer of the present invention is synthesized, for example, as follows: Allylamine and / or a salt thereof, a solvent and a polymerization initiator are put in a high-pressure gas polymerization vessel. In this case, an allylamine salt prepared in advance may be used, or an allylamine salt may be prepared by charging allylamine and an acid into a polymerization vessel. Solvents include, for example, water, methanol,
There are ethanol, acetone, benzene, toluene, hexane, DMF, DMSO, THF, ether, and chloroform.
As the polymerization initiator, a known radical polymerization initiator is used, and examples thereof include persulfates such as ammonium persulfate and potassium persulfate; 2,2′-diamidinyl-2,2′-azopropanedihydrochloride, azobisisobutyrate. Azo compounds such as ronitrile; di-t-butyl peroxide, cumene hydroperoxide, and peroxides such as hydrogen peroxide. The amount of the initiator is 0.01-based on the total monomer weight.
It is set to 10% by weight, preferably 0.1 to 1% by weight.

The pressure in the polymerization vessel containing allylamine and / or its salt, solvent and polymerization initiator is reduced, and vinyl chloride monomer is introduced. Then, the polymerization vessel is placed at 30 to 80 ° C, preferably 40
Heat to ~ 50 ° C to initiate polymerization. Polymerization time is 1 to 48
The time is preferably 3 to 12 hours. After completion of the polymerization reaction, the product is washed with water for several hours to remove unreacted allylamine monomer, allylamine salt monomer, homopolymers of these monomers and excess acid. Allylamine monomers, allylamine salt monomers, and homopolymers of these monomers are soluble in water and are easily removed by washing with water.

(Function) Since the vinyl chloride-allylamine-based copolymer of the present invention thus contains a repeating unit of allylamine or a salt thereof in the polymer chain, it is hydrophilic or not hydrophilic based on the amino group of allylamine or a salt thereof. In addition to having water absorption,
Highly conductive. Therefore, a vinyl chloride-based copolymer having excellent antistatic properties can be obtained. Further, since this copolymer has a highly reactive amino group, it is also used as a reactive resin.

(Examples) The present invention will be described below with reference to Examples.

Example 1 700 g of allylamine was dissolved in 9000 g of methanol and charged into a high-pressure polymerization vessel. This polymerization vessel was maintained at 10 ° C or lower, and 2550 g of phosphoric acid was added dropwise. Furthermore, t-butylperoxyneodecanoate 44 was added to this polymerization vessel as a polymerization initiator.
g was added. The pressure inside the polymerization vessel was reduced and 2400 g of vinyl chloride was introduced. The polymerization vessel was heated to 50 g and reacted for 10 hours.
After the completion of the polymerization reaction, the obtained polymer was washed with water for 2 hours to remove excess phosphoric acid and homopolymer of allylamine phosphate. After dehydrating the polymer after washing with water by centrifugation,
It was dried overnight at 40 ° C. Thus, 1870 g of vinyl chloride-allylamine / phosphate copolymer was obtained.

The obtained copolymer was a fine white powder and had a degree of polymerization of 310 as determined by a viscosity method. According to the elemental analysis of the copolymer, the content of N atom was 2.6% by weight. Thereby,
The unit of allylamine-phosphate in the copolymer was calculated to be 14.2 mol%.

This copolymer was dissolved in a mixed solvent of 60 g of tetrahydrofuran and 20 g of cyclohexanone and formed into a film by the solution casting method. The volume resistivity of this film was measured and found to be 8.3 × 10 ⁷ Ω · cm, indicating excellent conductivity.

Example 2 A vinyl chloride-allylamine / hydrochloride copolymer was prepared in the same manner as in Example 1 except that hydrochloric acid was used instead of phosphoric acid.
I got 1920g.

The obtained copolymer was a white powder and had a degree of polymerization of 250 as determined by a viscosity method. According to the elemental analysis of the copolymer,
The N atom content was 2.7% by weight. Therefore, the unit of allylamine hydrochloride in the copolymer was calculated to be 14.5 mol%.

This copolymer was formed into a film by the same method as in Example 1, and its volume resistivity was measured.
It was 0 ⁷ Ω · cm and had excellent conductivity.

Example 3 700 g of aylamine was dissolved in 9000 g of methanol and charged in a high-pressure polymerization vessel. To this polymerization vessel, 31 g of t-butylperoxyneodecanoate was added as a polymerization initiator. The pressure inside the polymerization vessel was reduced and 2400 g of vinyl chloride was introduced. Then, the same procedure as in Example 1 was carried out to obtain 200 g of a vinyl chloride-allylamine copolymer.

The obtained copolymer was a white powder and had a degree of polymerization of 350 as determined by a viscosity method. According to the elemental analysis of the copolymer,
The N atom content was 3.3% by weight. Thereby, the unit of allylamine in the copolymer was calculated to be 14.7 mol%.

This copolymer was formed into a film by the same method as in Example 1, immersed in water at 40 ° C. for 24 hours, and the water absorption was determined by the weight change. As a result, the water absorption rate was 6.1% by weight.

Comparative Example 1 1.8 g of t-butyl peroxyneodecanoate was dissolved in 9000 g of methanol and charged into a high-pressure polymerization vessel. The pressure inside the polymerization vessel was reduced, and 3600 g of vinyl chloride was introduced.
The reaction was carried out by solution polymerization for a period of time. The polymer obtained is 40
After drying at ℃ for 24 hours, 2750 g of vinyl chloride homopolymer was obtained.

The obtained homopolymer was a white powder and had a degree of polymerization of 410 by a viscosity method. This copolymer was formed into a film by the same method as in Example 1, and its volume resistivity was measured and found to be 1.6 × 10 ¹⁶ Ω · cm, indicating low conductivity. The water absorption of this film was measured in the same manner as in Example 3, and as a result, it was 0.03% by weight or less.

Comparative Example 2 1.8 g of t-butyl peroxy neodecanoate was dispersed in 9000 g of water together with 1.8 g of partially saponified polyvinyl alcohol (dispersant), and the mixture was charged into a high-pressure polymerization vessel. The pressure inside the polymerization vessel was reduced, 3600 g of vinyl chloride was introduced, and the suspension polymerization was carried out in the same manner as in Comparative Example 1. The obtained polymer was dried at 40 ° C. for one day to obtain 2850 g of vinyl chloride homopolymer.

The obtained homopolymer was a white powder and had a degree of polymerization of 1400 as determined by a viscosity method. This copolymer was formed into a film by the same method as in Example 1, and its volume resistivity was measured. As a result, it was 2.0 × 10 ¹⁶ Ω · cm, and the conductivity was low. The water absorption of this film was measured in the same manner as in Example 3, and as a result, it was 0.03% by weight or less.

As is clear from the examples and comparative examples, the vinyl chloride-allylamine-based copolymer of the present invention has water absorbency and excellent conductivity. If this copolymer has a phosphate or hydrochloride of an amino group, the volume resistivity is high and the conductivity is excellent, and if it has an amino group, the water absorption is high. Homopolymers of vinyl chloride have low volume resistivity and low water absorption, both of which are obtained by solution polymerization or suspension polymerization.

(Effect of the Invention) Since the vinyl chloride-allylamine-based copolymer of the present invention has excellent conductivity as described above, it has antistatic properties. This copolymer is also excellent in hydrophilicity and water absorption.
Moreover, since this copolymer has a reactive amino group in the skeleton, it also highly reacts with other compounds. It is also possible to modify the copolymer by reacting it with another functional compound. As a result, the copolymer of the present invention can be effectively used as a conductive sheet, a conductive coating material, a conductive treatment agent, an antistatic agent and the like.

Claims (2)

[Claims] 1. A molecular weight of 800 to 300,0 represented by the following formula:
00 vinyl chloride-allylamine copolymer: Here, m and n are each an integer of 1 or more,
And 0 <n ≦ (m + n) / 2, and R is an amino group and / or a Lewis acid of an amino group. 2. The Lewis acid is at least one of hydrochloride, sulfate, sulfite, phosphate, phosphite, hypophosphite, nitrate and nitrite. The vinyl chloride-allylamine copolymer according to item 1.