JP2677873B2 - Vinyl chloride copolymer and method for producing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a vinyl chloride copolymer having excellent surface water repellency, mechanical strength, roll processability, and the like.

[Conventional technology]

Conventionally, by homopolymerizing polypropylene oxide having a fluorinated hydrocarbon group at one end of the molecule and having a polymerizable unsaturated group at the other end, or by copolymerizing it with another copolymerizable monomer. It is known that a resin having excellent surface properties such as non-adhesiveness, leveling property, antistatic property, stain property, antifogging property and water / oil repellency can be obtained. The copolymerization of polypropylene chloride having a fluorinated hydrocarbon group at one end of the molecule and a polymerizable unsaturated group at the other end (hereinafter, also referred to as modified polypropylene oxide) with vinyl chloride is performed, for example. ,
It is known from JP-A-59-204144 and JP-A-61-266487. The above-mentioned JP-A-59-204144 discloses the following compound (A) as the modified polypropylene oxide.

[In the formula, Rf represents a C _{4 to} C ₂₀ fluoroalkyl group; R ₁ represents hydrogen or
C ₁ -C ₃ acyl group; R ₂ and C ₃ has one is hydrogen and the other is a methyl group; R ₄ is hydrogen or a methyl group; A is a divalent organic radical;
l, m and n are 0 to 40, respectively, and 0 <l + m +
Represents a number that satisfies n ≦ 40. JP-A-61-266487 discloses the following compound (B).

CH ₂ CRCR′COO (RO) _n Rf wherein Rf is a group containing a perfluoroalkyl group or a perfluoroalkylene glycol group, R is an alkylene residue, and R ′ is a hydrogen atom or a methyl group And n is a positive integer. The degree of polymerization of the compound (A) is at most 40. Also,
Although the polymerization degree of the compound (B) is described as a positive integer in the claims of the above publication, it is specifically 4
Only ~ 8 are disclosed.

[Problems to be solved by the invention]

DISCLOSURE OF THE INVENTION The inventors of the present invention have the following formulas as compounds representing the above compounds (A) and (B) for the purpose of improving vinyl chloride resin. Was copolymerized with a vinyl chloride monomer. The resin thus obtained is the above compound (C)
Although it has a relatively high water repellency when the content of the monomer unit based on (3) is 30 mol%, it has a drawback that the mechanical strength when formed into a film is too weak to be measured by a tensile strength tester. Therefore, the compound (C) has a function of modifying the surface properties of the vinyl chloride resin, but has not been put to practical use.

[Means for solving the problem]

In view of the above problems, the present inventors have studied for the purpose of improving the mechanical strength of the copolymer obtained by copolymerization with vinyl chloride monomer, as a result, the modified polypropylene oxide of a specific degree of polymerization The synthesis was successful, and it was found that the above problems could be solved by copolymerizing the modified polypropylene oxide and a vinyl chloride monomer, and the present invention was proposed.

That is, the present invention relates to the following formula [I] The vinyl chloride-based copolymer is characterized by comprising 5 to 60% by weight of the monomer unit represented by the following and 95 to 40% by weight of the vinyl chloride-based monomer unit.

JP-A-59-204144, which describes the compound (A), discloses only those having a degree of polymerization of up to 40,
There is no description about a compound having a polymerization degree of 70 to 350 corresponding to the monomer unit represented by the general formula [I] in the vinyl chloride copolymer of the present invention. Also, the degree of polymerization above 70
No disclosure is found in the above-mentioned publication at all, which suggests that the mechanical strength of the resin obtained by the copolymerization with the vinyl chloride monomer is remarkably improved by setting it to 350.

JP-A-61-2664 in which the other compound (B) is described.
Although the degree of polymerization n of the compound (B) is a positive integer in the claims of Japanese Unexamined Patent Publication No. 87, the detailed description of the invention specifically describes the degree of polymerization of 4 to 8. Things have not been dealt with. Further, as shown in Examples and Comparative Examples described later, the modified polypropylene oxide having a degree of polymerization of 17 has a tensile strength of 0 kg / copolymer with a vinyl chloride monomer.
cm ² is obtained by adjusting the polymerization degree to 70 to 350 like the monomer unit based on the modified polypropylene oxide represented by the general formula [I] in the vinyl chloride-based copolymer of the present invention. The vinyl-based copolymer exhibits a tensile strength of 100 kg / cm ² or more. Thus, in the present invention, the degree of polymerization of the monomer unit based on the modified polypropylene oxide represented by the general formula [I] in the vinyl chloride copolymer is 70 to 35.
By setting it to 0, the tensile strength of the vinyl chloride-based copolymer is dramatically improved, and a markedly excellent effect is exhibited. Such a description suggesting the excellent effect of the present invention is not recognized in the above-mentioned published patent publication. Therefore, the above-mentioned published patent publication only discloses the technical idea of the low molecular weight compound having a degree of polymerization of 4 to 8.

In the general formula [I], the number represented by n must be an integer of 70 to 350 in view of mechanical strength and surface properties when the vinyl chloride copolymer of the present invention is formed into a film. When n is less than 70, the mechanical strength of the film remarkably decreases, and when n exceeds 350, surface properties such as water repellency deteriorate, which is not preferable. Although n may be an integer shown in the above range, it is preferably an integer of 70 to 250 in consideration of the mechanical strength, surface properties, processability and the like of the vinyl chloride copolymer of the present invention.

In the general formula [I], as Rf, a fluorinated hydrocarbon group in which some or all of the hydrogen atoms of a hydrocarbon group are substituted with fluorine atoms is used without any limitation. For example, a fluorine-containing alkyl group, a fluorine-containing alkenyl group, a fluorine-containing alkynyl group,
Examples thereof include a fluorinated aryl group and a fluorinated aralkyl group. The number of carbon atoms in the fluorinated hydrocarbon group is not particularly limited, but is generally preferably selected from the range of 1 to 20, more preferably 3 to 15. Further, it is preferable that the ratio F / H of the fluorine atom to the hydrogen atom of the above-mentioned fluorine-containing hydrocarbon group is 1 or more, and more preferably 2 or more, because the surface properties of the vinyl chloride-based copolymer are both schools. In the present invention, as the fluorine-containing hydrocarbon group, a compound represented by the following formula Is a group represented by.

Polymerization degree n of the monomer unit represented by the general formula [I],
That is, variations in the molecular weight of the side chain portion can be reduced depending on the raw material used. For example, the molecular weight distribution represented by the ratio ( _w / _n ) of the weight average molecular weight ( _w ) and the number average molecular weight ( _n ) of the side chain portion can be 1.20 or less, and further 1.10 or less.

The ratio of the monomer unit represented by the general formula [I] and the monomer unit based on vinyl chloride must be 5 to 60% by weight for the former and 95 to 40% by weight for the latter. When the amount of the monomer unit represented by the general formula [I] is too small, the flexibility and surface water repellency of the film obtained from the vinyl chloride-based copolymer of the present invention are lowered, and conversely when it is too large. This is not preferable because the properties of polyvinyl chloride disappear and sufficient mechanical strength cannot be obtained. In order to make the flexibility, surface water repellency and mechanical strength of the film sufficient, the monomer unit represented by the general formula [I] is 20 to 50% by weight, and a vinyl chloride-based monomer is used. It is preferable that the unit is 80 to 50% by weight.

The vinyl chloride copolymer of the present invention generally has a degree of polymerization of 30,000 to 200,000. Further, the monomer unit represented by the general formula [I] and the monomer unit based on vinyl chloride are randomly arranged.

The vinyl chloride-based copolymer of the present invention generally exists as a white powder and dissolves in tetrahydrofuran, ethylene dichloride, etc., but does not dissolve only in swelling in solvents such as methanol and chloroform, and does not dissolve in water at all. Does not dissolve.

The structure of the vinyl chloride-based copolymer of the present invention has a structure of'H-nuclear magnetic resonance spectrum (hereinafter, simply referred to as'H-NMR), ¹⁹ F
-Nuclear magnetic resonance spectrum (hereinafter simply referred to as ¹⁹ F-NMR)
It can be confirmed by an infrared absorption spectrum (hereinafter, simply referred to as IR).

Further, the degree of polymerization n of the monomer unit represented by the above formula [I]
Is X Consists of this combination for what is The number average molecular weight ( _n ) is obtained by hydrolyzing the unit and using the degradation product by gel permeation and chromatography (hereinafter simply referred to as GPC), and the molecular weight of the terminal fluorinated hydrocarbon group is calculated from this value. Can be calculated by dividing the value by dividing the value by the molecular weight of the propylene oxide monomer unit.

With respect to those in which X is —CH ₂ —, the above hydrolysis method cannot be used, and therefore the degree of polymerization n cannot be directly obtained from the monomer unit represented by the above [I]. .
In this case, it can be obtained using the following indirect method.

That is, the composition of each monomer unit in the vinyl chloride-based copolymer determined by'H-NMR is used to determine the weight Fw ₁ of polypropylene oxide in 1 g of the copolymer. Next, the number l contained in 1 g of the fluorinated hydrocarbon group copolymer is determined from the value of elemental analysis. Using these values, the degree of polymerization n of the monomer unit in the formula [I] can be determined by the following formula.

(However, Fw ₂ is the molecular weight of the propylene oxide monomer) The vinyl chloride-based copolymer of the present invention may be produced by any method, but generally, the following method is preferably adopted.

That is, the following general formula [III] Is a method of polymerizing vinyl chloride in the presence of a compound represented by.

The compound represented by the above formula [III] used in the present invention is a porphyrin-aluminum complex as a catalyst, and propylene oxide is polymerized in the presence of a fluorine-containing active hydrogen compound. It can be obtained by reacting with a halide or the like.

The polymerization of vinyl chloride in the present invention is preferably suspension polymerization. Suspension polymerization can be performed using the following radical polymerization initiators. For example, lauroyl peroxide, benzoyl peroxide, azobisisobutyronitrile, diisopropyl peroxycarbonate, te
It is an oil-melting radical polymerization initiator such as rt-butyl perpivalate. These initiators are 0.01 to
It is preferable to use it in the range of 5% by weight.

In addition, in the polymerization of the present invention, it is preferable to add a dispersant in order to prevent blocking of polymer particles generated as in the case of general suspension polymerization. Specific examples of suitable dispersants include synthetic or natural polymer compounds such as polyvinyl alcohol, partially saponified polyvinyl alcohol, hydroxycellulose, methylcellulose, starch and gelatin; calcium, barium, aluminum, strontium and magnesium. A phosphate etc. can be mentioned. Particularly preferred are polyvinyl alcohol and partially saponified polyvinyl alcohol.

Although the addition of a surfactant or the like is not necessary in the present invention, it can be used.

Also, the amount of water used as a solvent is 50 per 100 g of vinyl chloride.
It is preferably in the range of up to 500 cc, more preferably 70 to 300 cc.

Further, the weight composition of the compound of general formula [III] and vinyl chloride is preferably 5/95 to 50/50 in order to keep the composition of the copolymer within the above range.

Regarding the polymerization temperature, it is necessary to select a suitable temperature depending on the kind of the initiator to be used and the composition to be charged, but it is generally 30
It is preferably -80 ° C. In particular, 40 to 60 ° C. is preferable from the viewpoint of controlling side reactions.

The polymerization time varies depending on the activity of the initiator and the polymerization temperature, but is generally 3 to 10 hours.

The stirring speed at the time of polymerization influences the dispersion of the polymer particles produced and the like, so it is preferably carried out at a constant rotation speed selected from the range of 400 to 700 rotations / minute. The vinyl chloride-based copolymer obtained by the polymerization of the present invention is fine particles having a uniform white particle size, and can be easily isolated by passing it. The compound represented by the general formula [III] which remains unpolymerized in the polymer particles can be easily removed only by washing with methanol, and the removal can be confirmed by gel permeation chromatography. It can be done by graphy.

The vinyl chloride-based copolymer obtained in the present invention can be processed into a film by using a hot roll machine. The temperature of the roll surface needs to be set to an optimum temperature depending on the composition of the vinyl chloride copolymer. Generally 50
The temperature can be selected from the range of up to 200 ° C, particularly preferably 100 to 180 ° C.

At this time, a metal such as an organic tin-based stabilizer represented by dibutyl tin malate-based stabilizer as a heat stabilizer, a lead-based stabilizer, a cadmium-based stabilizer, a barium-based stabilizer, a zinc-based stabilizer, a calcium-based stabilizer, etc. It is preferable to add a stabilizer in an amount of 1 to 10% by weight, preferably 2 to 6% by weight.

(Effect)

The vinyl chloride-based copolymer of the present invention has sufficient mechanical strength for practical use, and has good surface water repellency and other properties. Further, it has sufficient flexibility without using a plasticizer, is excellent in roll processability, and is also excellent in transparency.

Further, as the compound represented by the general formula [III] which is a raw material for producing the vinyl chloride-based copolymer of the present invention, the ratio ( _w / _w ) of the weight average molecular weight ( _w ) to the number average molecular weight ( _n )
_When the narrow molecular weight distribution represented by _n ) is 1.20 or less and 1.10 or less, it has the following advantages. In the compound represented by the general formula [III], the polymerization activity of the polymerizable unsaturated group at one end of the molecule differs depending on the molecular weight. Therefore, when a compound having a wide molecular weight distribution is used as the compound represented by the general formula [III], the copolymerizability with vinyl chloride varies. However, when the compound represented by the above general formula [II] having a narrow molecular weight distribution is used, the copolymer with vinyl chloride proceeds uniformly, and the physical properties of the obtained vinyl chloride copolymer do not vary.

Further, when a compound having a narrow molecular weight distribution is used as the compound represented by the general formula [III], the low molecular weight component is scarcely contained because the compound has a large molecular weight. Therefore, in the copolymerization with vinyl chloride, it is possible to prevent the generation of the solvent-insoluble component due to the chain transfer reaction (side reaction) due to the presence of the low-molecular weight component.

The vinyl chloride-based copolymer of the present invention has a structure in which the molecular chain of polypropylene oxide is branched from the main chain. By increasing the degree of polymerization of the side chain branched from the main chain to a specific value instead of increasing the degree of polymerization of the main chain, it was possible to dramatically improve the mechanical strength of the vinyl chloride copolymer. It is amazing.

The vinyl chloride-based copolymer of the present invention having the above-mentioned excellent properties can be used for various purposes such as interior materials for construction, roofing materials, marking films, mold release materials, blood bags and the like. Further, from the temperature dependence data of the viscoelastic behavior, it can be used as a soundproofing film or a sound deadening material.

〔Example〕

The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

The physical properties of the film-processed sample were measured by the following methods.

1. Mechanical Properties Tensile strength (kg / cm ² ) was measured.

2. Surface water repellency The contact angle of water (1 minute after contact with water at 25 ° C and 50% humidity) was measured.

3. Transparency The transmittance (%) of light having a wavelength of 500 mμ was measured and evaluated according to the following criteria.

Good Good 85% or higher Fairly good 70 to 85% Fairly bad 55 to 70% Poor 55% or less 4. Roll formability Small thermal roll machine (5RK4, manufactured by Oriental Motor Co., Ltd.)
(0RGN A type) was used to roll the vinyl chloride-based copolymer, and evaluation was performed at the highest roll surface temperature at which roll processing was possible.

Good 130 ℃ or more Slightly good 100-130 ℃ Poor 100 ℃ or less Examples 1-4 General formula below In the compound [A] represented by the formula (1), n and Rf are the numbers or groups shown in Table 1, and 60 g of a compound and 1.22 g or 2.44 g of diipropylperoxycarbonate which is a radical polymerization initiator are mixed, and further mixed with a dispersant. 4.16 ml of an aqueous solution having a partially saponified polyvinyl alcohol concentration of 4.14% was added, and these mixed solutions were added to one autoclave. Then water 220c
The system was sealed by adding c, and the atmosphere was replaced with nitrogen. Next, 103 cc of vinyl chloride monomer was added, and the whole system was stirred at 500 rpm. Further, constant temperature water was circulated from an external circulation tank to carry out polymerization at 50 ° C. for 5 hours.

Next, the vinyl chloride-based copolymer obtained in each example was isolated, washed with methanol, and it was confirmed by GPC that the peak of the compound [A] was not detected. After that, 'H-NM
The structure was confirmed by R, ¹⁹ F-NMR, IR and GPC (second
table).

Further, the compound [A] contained in the vinyl chloride-based copolymer
In order to obtain the number n of propylene oxide chains of the monomer unit based on, the vinyl chloride-based copolymer (5 g) was mixed with 50 ml of tetrahydrofuran, 10 ml of water, and 2.5 g of potassium hydroxide.
The hydrolysis reaction was performed under reflux conditions for a time. After the reaction,
Water and tetrahydrofuran were distilled off under reduced pressure, the decomposed product was extracted with chloroform, washed with water, and then dried over sodium sulfate. Then, chloroform was distilled off to obtain a pale yellow viscous fluid. When this fluid was analyzed by'H-NMR, a peak derived from polypropylene oxide was detected. Further, GPC analysis of this substance revealed that each had a molecular weight as shown in Table 2. Therefore, the value obtained by subtracting the molecular weight of the terminal fluoroalkyl group from this molecular weight is divided by the molecular weight (58) of the propylene oxide monomer unit to obtain the above n.
I was able to ask. The value of the degree of polymerization n is also shown in Table 2.

The degree of polymerization of the chloroform extract obtained by the hydrolysis and the degree of polymerization of the compound [A] used for the polymerization were almost the same within the experimental error.

The IR spectrum chart, 'H-NMR chart and ¹⁹ F-NMR chart of the compound obtained in Example 1 are shown in FIGS. 1, 2 and 3, respectively.

To the vinyl chloride-based copolymer thus obtained, 4% by weight of dibutyltin malate was added, and a small-sized hot roll process was performed to prepare a film.

The roll processability, mechanical strength, surface water repellency and transparency of the film are shown in Table 3. Further, none of the vinyl chloride-based copolymers had an insoluble content in tetrahydrofuran at 66 ° C.

Comparative Example 1 The polymerization reaction was carried out in the same manner as in Example 1 except that the compound [A] having the following structure was used.

The resulting copolymer was insoluble in all solvents.

Comparative Example 2 The polymerization reaction was performed in the same manner as in Example 1 except that the compound [A] having the following structure was used.

Using the obtained copolymer, a film was prepared by a heat roll, and its physical properties were measured and are shown in Table 3 together.

Examples 5-8 Compounds [A] represented by the general formula used in Examples 1 to 4
Polymerization was carried out in the same manner as in Example 1 with the amount of the vinyl chloride monomer charged to the value shown in Table 4. These polymerization conditions are shown in Table 4.

Next, the structure of the vinyl chloride-based copolymer obtained by this polymerization was confirmed by the method shown in Examples 1 to 4. The results are shown in Table 5.

The vinyl chloride-based copolymer thus obtained was used to form a film, and its physical properties were measured and are shown in Table 6. None of the vinyl chloride-based copolymers was insoluble in 66 ° C tetrahydrofuran.

The'H-NMR chart of each vinyl chloride type copolymer is shown in FIG.

Examples 9 to 13 Compounds [A] represented by the general formula used in Examples 1 to 4
Polymerization was carried out in the same manner as in Example 1 by changing the kind of the hydrogen fluoride group Rf and the kind of the initiator. The polymerization conditions are shown in Table 7.

Next, the structure of the vinyl chloride-based copolymer obtained by this polymerization was confirmed and the physical properties of the film were measured by the same method as in Examples 1 to 4. The result is the eighth
The results are shown in Tables and 9. None of the vinyl chloride-based copolymers was insoluble in 66 ° C tetrahydrofuran.

Examples 14 to 15 Polymerization was performed in the same manner as in Example 1 except that the terminal methacryloyl group of the compound [A] used in Examples 1 to 4 was changed to an acryloyl group and an allyl group. I did. The polymerization conditions are shown in Table 7, and the structural confirmation of the obtained vinyl chloride-based copolymer and the physical property measurement results of the film are shown in Tables 8 and 9, respectively. None of the vinyl chloride-based copolymers was insoluble in 66 ° C tetrahydrofuran.

[Brief description of the drawings]

1, FIG. 2 and FIG. 3 are infrared absorption spectra of the vinyl chloride copolymer obtained in Example 1, respectively.
A nuclear magnetic resonance spectrum and a ¹⁹ F-nuclear magnetic resonance spectrum are shown. FIG. 4 shows the'H-nuclear magnetic resonance spectra of the vinyl chloride copolymers obtained in Examples 5-8.

Claims (2)

(57) [Claims] 1. A compound of the formula [I] A vinyl chloride-based copolymer comprising 5 to 60% by weight of a monomer unit represented by and 95 to 40% by weight of a vinyl chloride-based monomer unit. 2. The general formula [II] The method for producing a vinyl chloride-based copolymer according to claim (1), characterized in that vinyl chloride is polymerized in the presence of a compound represented by the formula (1).