JPH11158219A - Chlorinated vinyl chloride-based resin and its preparation - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject resin having excellent gelation property and heat resistance by finely pulverizing a vinyl chloride-based resin in the granule state with a specific particle dia., thereafter chlorinating it. SOLUTION: This preparation comprises disintegrating or pulverizing a vinyl chloride-based resin into a dimension of a vol.-average particle dia. of 0.5-50 μm, thereafter chlorinating it. A unit particle of the vinyl chloride-based risin after the atomization is pref. a microparticle which has been disintegrated or pulverized into an agglomerate particle of a primary particle. The vinyl chloride-based resin before the pulverization has 1.3-8 m<2> /g of a BET specific surface area and has pref. more than 0.6 of a peak ratio [(chlorine atom peak) ×2/carbon atom peak] in the IS bond energy value (eV) between a carbon atom and a chlorine atom, in a particle surface analysis by an electron spectrochemical analysis. Disintegration or pulverization of the vinyl chloride- based resin is carried out pref. in the presence of 5-30 pts.wt. of an aq. medium on the basis of 100 pts.wt. of the resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a chlorinated vinyl chloride resin and a method for producing the same.

[0002]

2. Description of the Related Art Vinyl chloride resin (hereinafter also referred to as PVC) is used in many fields as a material having excellent mechanical strength, weather resistance and chemical resistance. However, since the heat resistance is poor, chlorinated vinyl chloride resin (hereinafter referred to as CPVC) having improved heat resistance by chlorinating PVC.
) Has been developed.

[0003] PVC has a low heat distortion temperature and the maximum usable temperature is around 60 to 70 ° C, so that it cannot be used for hot water, whereas CPVC has a heat deformation temperature of 20 to 40 ° C than PVC. Therefore, it can be used for hot water, and is suitably used for heat-resistant pipes, heat-resistant joints, heat-resistant valves, and the like.

However, since CPVC has a high heat deformation temperature, a high temperature and a strong shearing force are required for gelling at the time of molding processability, and it tends to be decomposed and colored during molding. Therefore, CPVC is often produced in a narrow molding process width and in an insufficiently gelled state,
The performance of the material was not fully demonstrated. Further, in addition to the demand for improving the gelation performance, higher heat resistance is also required.

In order to solve such problems, for example, Japanese Patent Application Laid-Open No. 49-6080 discloses a method of using a suspension stabilizer comprising an ionic emulsifier, a water-soluble metal salt and a water-soluble polymer dispersant. Discloses a method of chlorinating PVC composed of aggregates composed of basic particles of about 1 μm (improvement of resin particles). However, in this method, the gelling performance at the time of molding has been improved, but it is not yet sufficient, and a large amount of scale is generated at the time of polymerization, which adheres to the wall surface of the polymerization tank to reduce the heat removal effect. There is a problem that the scale removal operation is required for the inhibition.

Similarly, for example, Japanese Patent Application Laid-Open No. 62-915
No. 03 discloses P which is emulsion polymerized in the presence of a surfactant.
A method for chlorinating VC is disclosed. (Improvement of resin particles by polymerization). However, since a large amount of an emulsifier is used in emulsion polymerization, a large amount of a substance that is chlorinated itself and hinders chlorination of the resin particles themselves adheres to the surface of the PVC particles, so that heat resistance is high. However, there was a problem that was not improved.

[0007] JP-A-5-132602 discloses a CP.
There is disclosed a method of blending VC and PVC so as to be within a specific viscosity range to obtain high heat resistance (improvement by resin blending). However, in this method,
It is possible to expect improvement of heat resistance of about 3-4 ° C in Vicat value and slight improvement of gelation performance by improvement of melt viscosity. Did not achieve.

[0008] JP-A-6-128320 discloses PV
As a chlorination method of C, a chlorination method by two steps (two-step post-chlorination method) is disclosed. This method
By increasing the chlorine content to 70-75% by weight,
It is intended to obtain a CPVC having high heat resistance (an improvement proposal by a high chlorination method). However, in this method, although high heat resistance can be expected according to the chlorine content, no means has been shown for preventing the deterioration of the gelation performance predicted by high chlorination,
High heat resistance and gelation performance were not achieved on a practical level.

In Japanese Patent Application Laid-Open No. 1-217008, the range of the average particle diameter and the porosity of the PVC resin is limited in the photochlorination reaction method by intermittent irradiation. This proposal aims to make the chlorination reaction uniform within the resin particles by promoting the diffusion of chlorine in the non-irradiation step. However, since the surface properties (skin layer) of the resin particles are not considered, the heat resistance of the obtained CPVC is improved, but the gelation performance has not been improved.

Japanese Patent Publication No. 57-501184 discloses a chlorination reaction method using actinic radiation using liquid chlorine as a main component of a chlorine source, in which the average particle size of granular resin particles is 10 to 50 μm as PVC. And the average particle diameter of the primary particles, which is a component of the particles, is 0.05 to 5 μm, and the porosity of the resin particles is 0.2 to 0.3.
A method for manufacturing CPVC using VC is disclosed. This technique focuses on the resin particle diameter and the primary particles because the diffusion process of chlorine in the central nucleus of the PVC particles to be chlorinated can be rate-limiting in the chlorination reaction of PVC. The degree of improvement in heat resistance and gelling performance of CPVC was low. Because
"AIChE Journal; oct. 1988, V
ol. 34, no. 10, p. 1683-1690 ", the diffusion of chlorine in the chlorination reaction is not determined in elementary units called primary particle diameter or grain diameter, but the agglomerate diameter in which the primary particles are bonded is present. It is considered to be dominant.

However, it is not possible to obtain CPVC excellent in heat resistance and gelling performance only by finding that the agglomerate diameter is dominant. The reason is PV
In C, a dispersant is used at the time of suspension polymerization, so that the grain particles have a thick skin layer, and the presence of this skin layer lowers the gelling performance and further inhibits the diffusion of chlorine. Because it can be done. That is, in order to obtain CPVC excellent in heat resistance and gelling performance, it is necessary to pay attention to both the skin layer and the agglomerate diameter.
It is very difficult to remove the skin layer and control the agglomerate diameter from the conventional CP.
None of the two methods were studied in the production method of VC.

[0012]

DISCLOSURE OF THE INVENTION In view of the above, the present invention provides a method of finely pulverizing PVC resin particles, and provides excellent gelation performance and heat resistance by chlorinating the PVC. An object is to provide a CPVC and a method for manufacturing the same.

[0013]

Means for Solving the Problems The invention of claim 1 (hereinafter referred to as "the invention")
The present invention 1) is a CPVC obtained by chlorinating PVC.
Wherein the PVC has a volume average particle diameter of 0.5 to 50.
It is characterized by being crushed or crushed to a size of μm and then chlorinated.

The invention of claim 2 (hereinafter, referred to as invention 2)
Is a CPVC obtained by chlorinating PVC, wherein the PVC is
It is characterized in that VC is crushed or crushed to a size corresponding to agglomerate particles, which are aggregates of primary particles, and then chlorinated.

[0015] The invention of claim 3 (hereinafter referred to as invention 3)
The PVC according to the present invention 1 or 2 has a BET specific surface area value of 1.3 to 8 m ² / g and, in the particle surface analysis by electron spectrochemical analysis, shows a value of 1% between carbon atom and chlorine atom.
The peak ratio [(chlorine atom peak) × 2 / carbon atom peak] in the S bond energy value (eV) exceeds 0.6.

The invention of claim 4 (hereinafter referred to as the present invention 4)
Is a CPVC obtained by chlorinating PVC, wherein the PVC is
VC has a BET specific surface area of 1.3 to 8 m ² / g, and in a particle surface analysis by electron spectrochemical analysis, a peak ratio of carbon atoms to chlorine atoms in a 1S bond energy value (eV) [(chlorine Atom peak) × 2 / carbon atom peak] exceeds 0.6, and the PV
Agglomerate which is an aggregate of primary particles of C having a volume average particle diameter of 1 to 7 μm is chlorinated.

The invention of claim 5 (hereinafter referred to as the present invention 5)
Can be used to transfer PVC together with an aqueous medium to a volume average particle size of 0.5 to
The method according to any one of claims 1 to 4, wherein the PVC is crushed or crushed to a size of 50 µm and the PVC is chlorinated. Hereinafter, the present invention will be described in detail.

In the conventional CPVC and the production method thereof, when chlorinating PVC, attention is not paid to the surface state and the internal state of the PVC particles.
No attention was paid to the chlorination distribution state of the obtained CPVC. In the present invention, by focusing on the surface state and internal state of PVC, and further focusing on the chlorination distribution state of the obtained CPVC, a CPVC excellent in gelation performance and heat resistance is obtained.

The PVC of the present invention is a PVC polymerized by suspension polymerization or bulk polymerization. The CPVC of the present invention and the method for producing the same are obtained by chlorinating the above PVC.

The above PVC is a vinyl chloride monomer alone,
Alternatively, it is a resin obtained by polymerizing a mixture of a vinyl chloride monomer and another monomer copolymerizable with the vinyl chloride monomer by a known method. The other monomer copolymerizable with the vinyl chloride monomer is not particularly limited, and examples thereof include alkyl vinyl esters such as vinyl acetate; α-monoolefins such as ethylene and propylene; vinylidene chloride; Is mentioned. These may be used alone or in combination of two or more.

The average degree of polymerization of the PVC is not particularly limited, and those generally used in the range of 400 to 3000 can be used.

PVC used in the present invention 1, 2 and 5
Is not particularly limited with respect to surface characteristics, skin structure, and the like.

According to the present invention, the fine particles of P
The volume average particle diameter of VC is limited to between 0.5 and 50 μm. The reason for this is that after chlorine diffuses in the chlorination reaction,
Although the displacement reaction with hydrogen proceeds, in order for chlorine diffusion to proceed smoothly as compared with unpulverized ordinary PVC, the volume average particle diameter needs to be 50 μm or less. The size of the primary particles is about 0.5 to 2 μm, and it is difficult to make the particles smaller than this size. The volume average particle diameter is more preferably in the range of 10 to 30 μm from the efficiency of pulverization and the smoothness of chlorine diffusion.

It is preferable that the particle unit of PVC after the fine particle formation according to the second aspect of the present invention is a fine particle which is disintegrated or pulverized to agglomerate particles which are aggregates of primary particles. The reason is that disintegration to the agglomerate particle level or pulverization is relatively easy, and in addition to the large processing capacity in the disintegration step, the chlorine is diffused in the chlorination reaction in the same manner as described above, and then hydrogen and In order for the substitution reaction to proceed, but for the diffusion of chlorine to proceed smoothly compared to unground pulverized ordinary PVC, the collapse to the level of agglomerate particles, which is an aggregate of primary particles, or the pulverized fine particles Is preferable.

In general, it is known that a vinyl chloride resin has a similar hierarchical structure in its particle structure (“Polyvinyl chloride resin—its basis and application”, 2).
14-218 (edited by Kinki Chemical Association Vinyl Subcommittee, published by Nikkan Kogyo Shimbun, 1988). The agglomerates are agglomerates due to weak binding of primary particles in such a hierarchical creation. The particle size of the agglomerate is determined by a commercially available scanning electron microscope (hereinafter, referred to as SEM).
Or observed with a transmission electron microscope (hereinafter referred to as TE),
The size can be measured by photographing, etc.
The presence of agglomerates in collapsed fine particles is also SEM
Can be confirmed by That is, after confirming the size of the agglomerate of the PVC particles from the fractured SEM photograph of the PVC particles before collapse, the particles of the size smaller than the agglomerate particles are recognized and identified from the SEM photograph of the fine particles,
By image analysis, it is possible to calculate the area occupied by particles smaller than agglomerate particles in the photograph. When the occupied area ratio of the agglomerate particles thus obtained is 95% or more, it is determined that the fine particles have been broken down into agglomerates.

The surface properties of PVC used in the present inventions 3 and 4 are such that uniform chlorination can be performed and
In order to exhibit excellent thermal stability, its BET specific surface area value is preferably 1.3~8m ² / g, 2~6m ² /
g is more preferred. The BET specific surface area value is 1.3 m ² /
When the amount is less than 0.1 g, the number of fine pores of 0.1 μm or less in the PVC particles is reduced, so that chlorination is not performed uniformly. As a result, the heat resistance of the obtained CPVC does not improve, and
If it exceeds m ² / g, the heat resistance of the PVC particles themselves before chlorination decreases, and the workability of the obtained CPVC deteriorates.

The PVC used in the present inventions 3 and 4 has a peak ratio [(chlorine atom peak) at 1S bond energy value (eV) of carbon atom and chlorine atom in particle surface analysis by electron spectrochemical analysis (ESCA analysis). ) × 2 /
Carbon atom peak) is preferably more than 0.6,
More than 0.7 is more preferred. 0.6 peak ratio
If it is below, it is considered that an additive such as a dispersant is adsorbed on the surface of the PVC particles, so that not only the chlorination rate in the subsequent step is reduced, but also a problem occurs in the molding processability of the obtained CPVC. .

Among the PVC having a peak ratio of more than 0.6, particles having a small surface area (hereinafter, referred to as skin) on the surface of the PVC particles and exposing a fine structure (primary particles) inside the particles ( Skinless PVC). If the energy ratio is the same, it is preferable to use skinless PVC.

The atomic abundance in the chemical structure of PVC is as follows:
Chlorine atom: carbon atom = 1: 2 (when the terminal structure and branching are not considered), and the peak ratio (chlorine element peak × 2 / carbon element peak) in the above 1S binding energy value (eV) is 0 to 1. Becomes If the peak ratio is 0, PV
It means that the surface of the C particles is covered with other substances other than PVC and does not contain chlorine. When the peak ratio is 1, the surface of the PVC particles is completely covered with only the vinyl chloride component. Means that

The above-mentioned PVC having a BET specific surface area value, a peak ratio at 1S binding energy value (eV), and an average particle size of agglomerate can be used, for example, as a dispersant with a high degree of saponification (60 to 90 mol%). ) Or a low saponification degree (20 to 60 mol%) or both of them by adding water-suspension polymerization of polyvinyl acetate, higher fatty acid esters and the like by adding an anionic emulsifier, a nonionic emulsifier and the like as an emulsifier. be able to.

The agglomerate diameter, which is an aggregate of the primary particles of the PVC of the present invention 4, is preferably 1 to 7 μm, more preferably 1.5 to 7 μm.
-5 μm is more preferable. Agglomerate diameter is 1μm
If it is less than 7, the scale adheres to the polymerization vessel wall during the production of PVC, and the fine powder of the resin powder increases, which hinders the handling. If it exceeds 7 μm, the diffusion of chlorine during chlorination becomes difficult. The chlorination reaction becomes diffusion-controlled, and the chlorination distribution becomes too wide.
C cannot be expected to have improved heat resistance, and furthermore, a large amount of energy is required to disintegrate the agglomerate particles. Therefore, the gelling performance of the obtained CPVC is not improved. The agglomerate diameter can be measured by observing with a TEM or SEM and measuring the size by photographing.

The apparatus for disintegrating or crushing PVC mainly includes a hopper section for continuously supplying PVC into the apparatus, a particle crushing section, a transport section for crushed resin, and an aqueous medium for supplying PVC to the apparatus. It is composed of a pipe that can be supplied at a constant weight ratio to the resin. Each device is accompanied by a heating part capable of controlling the temperature required for disintegration or crushing, and terminals and a control system required for controlling the temperature. Further, a batch-type kneader may be used as an apparatus for disintegrating or pulverizing PVC.

As the above-mentioned pulverizing apparatus, an apparatus which has little local shearing action and can apply uniform shear to the resin is preferable. Further, in order to prevent the resin from gelling due to heat generated by kneading, an apparatus having high cooling efficiency is used. Is suitable. As such an apparatus, for example, BUSS (Switzerland)
"Kneader", "KCK kneader" manufactured by KCK (Japan) and the like.

In the present invention 5, an aqueous medium is used in the process of disintegration or pulverization of PVC, and the aqueous medium reduces the shearing force required for pulverizing PVC particles and effectively prevents local heating generated during pulverization. And effectively transfer the heat to the unmilled particles. The amount of the aqueous medium is preferably 5 to 30 parts by weight, more preferably 10 to 20 parts by weight, based on 100 parts by weight of PVC. If the amount of the aqueous medium is less than 5 parts by weight, the crushing power required for crushing the particles is excessively large, which is not preferable. Furthermore, since the local heating during the pulverization cannot be sufficiently removed, the resin is liable to undergo thermal decomposition, and there is a possibility that the physical properties may be reduced due to generation of hydrochloric acid, partial coloring or decomposition. If the amount of the aqueous medium exceeds 30 parts by weight, the aqueous medium is substantially contained above the surface moisture of the PVC particles, so that the aqueous medium is separated from the resin, and the aqueous medium does not work effectively. Further, the heating temperature required for pulverizing the resin is not reached due to the excess aqueous medium, which is not preferable.

In order to remove the monomer and remove the aqueous medium after suspension polymerization of PVC, the resin from which the aqueous medium is separated by a centrifugal dehydrator is usually 15 to 30 parts by weight per 100 parts by weight of the resin. Aqueous medium. Therefore, after the suspension polymerization, the monomer is removed, and the aqueous medium is removed by a centrifugal dehydrator, and then supplied to the pulverizing device exemplified in the present invention to produce fine particles within the scope of the present invention. Can be.

The shape and structure of the polymerization vessel (pressure-resistant autoclave) that can be used for the polymerization of PVC are not particularly limited, and those conventionally used for polymerization of PVC can be used. In addition, the stirring blade is not particularly limited, and includes, for example, those generally used such as a Faudler blade, a paddle blade, a turbine blade, a fan turbine blade, and a bull margin blade. Used for baffles
Is not particularly limited.

The method for chlorinating PVC is not particularly limited, and it can be carried out by various conventionally known methods. For example, it can be performed by bringing the above PVC into a suspended state, a state of being dissolved in a solvent or a solid state, and then contacting it with chlorine. Among the above methods, when chlorination is carried out particularly in a suspended state, the chlorination is carried out by blowing chlorine directly into the suspension itself without separating PVC obtained by suspension polymerization from an aqueous medium. It can be carried out.

In the case of chlorination in the above suspended state, for example, a method of irradiating the reaction product with light to accelerate chlorination in a photoreactive manner, or by exchanging heat with resin to excite the bonding of the resin and chlorination. Can be carried out by a method that promotes Light sources for chlorination by light energy include, for example, ultraviolet rays; mercury lamps, arc lamps, incandescent lamps, fluorescent lamps,
Visible light such as a carbon arc is exemplified. Of these, ultraviolet light is effective. In the case of chlorination by thermal energy, examples of the heating method include an outer jacket method, an inner jacket method, and a steam blowing method from the reactor wall. Of these, the outer jacket method and the inner jacket method are effective.

In the present invention, the chlorination is preferably carried out mainly by a heat energy source. Chlorination mainly using the above thermal energy source,
This is a method of promoting chlorination by exciting resin bonds and chlorine by thermal energy. In order to achieve uniform chlorination,
It is necessary to make the chlorination reaction uniform at the same time as making the chlorine diffusion uniform. Here, the heat energy acts uniformly inside the particles, but the light irradiation energy effect is limited to the surface of the resin particles, so that the chlorination reaction inevitably increases on the surface of the resin particles. Therefore, in order to realize uniform chlorination in diffusion and reaction, it is preferable to perform chlorination mainly using a heat energy source.

The aqueous medium used for chlorination in the suspended state may further contain, if necessary, a small amount of ketones such as acetone and methyl ethyl ketone; a small amount of chlorine such as hydrochloric acid, trichloroethylene and carbon tetrachloride. A system solvent may be added.

The chlorination reaction is preferably carried out by adjusting the chlorine content of the obtained CPVC to 60 to 72% by weight. More preferably, it is 63 to 70% by weight.

[0042]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

(Example 1) [Preparation of PVC] In a polymerization vessel (pressure-resistant autoclave) having an internal volume of 100 liters, 50 kg of deionized water and vinyl chloride monomer were partially saponified polyvinyl acetate (average saponification degree). 450 ppm, sorbitan monolaurate 1,800 ppm, lauric acid 1,200 ppm, polyacrylamide (20 ° C., 1a)
200 ppm of a 0.1 wt% aqueous solution at tm (with a Brookfield viscosity of 51 cps) and 550 ppm of t-butylperoxy neodecanoate.
Next, after degassing the inside of the polymerization vessel to 45 mmHg, 33 kg of a vinyl chloride monomer was charged and stirring was started.

The polymerization was started by raising the temperature of the polymerization vessel to 57 ° C.
This temperature was maintained until the end of the polymerization reaction. Polymerization conversion rate is 90
%, The reaction was terminated, and the unreacted monomer in the polymerization vessel was recovered. Then, the polymer was taken out of the system in the form of slurry, and dehydrated and dried to obtain PVC. BE of the obtained PVC
The T specific surface area value was 4.1 m ² / g. The ESCA analysis value indicating the extent of the presence of the skin layer was 0.85. The measurement of the BET specific surface area and the ESCA analysis were performed by the following methods.

[Disintegration of PVC] The above-obtained PVC was kneaded with a kneader “BUS Kneader Model KKG-4.6-”.
No. 7, 30 kg was supplied per hour. The inner wall of the barrel of the kneader was adjusted to 60 ± 3 ° C. through oil whose temperature was controlled to 60 ° C. in advance. The kneading was performed under the conditions shown in Table 1. The screw is a single-screw extruder having a diameter of 46 mm, and has a mechanism of repeating a reciprocating motion once back and forth for each rotation of the screw. The collapsed and pulverized PVC is transferred to a suspension / dispersion storage tank while appropriately adding an aqueous medium. Finally, an aqueous medium 4 is prepared with respect to PVC1 (weight ratio). PV in this state
The volume average particle diameter of C was measured, and the results are shown in Table 1.
The agglomerate occupied area ratio was 99%. still,
The measurement of the volume average particle diameter and the determination of the miniaturization of agglomerate were performed by the following methods.

[Preparation of CPVC] The above-mentioned hydrated PVC 200 was placed in a reaction vessel made of glass lining having an internal volume of 300 liters.
kg (composed of 40 kg of PVC and 160 kg of aqueous medium) were charged and stirred to disperse the PVC in water, and then the temperature of the reaction vessel was raised and kept at 110 ° C. Next, nitrogen gas was blown into the reaction tank, and the inside of the tank was replaced with nitrogen gas. Then, chlorine gas was blown into the reaction tank to chlorinate PVC. The chlorination reaction was continued while measuring the hydrochloric acid concentration in the tank to check the progress of the chlorination reaction, and when the chlorine content of the generated CPVC reached 68.0% by weight, the supply of chlorine gas was stopped. Then, the chlorination reaction was completed. Furthermore, nitrogen gas was blown into the tank to remove unreacted chlorine, and the obtained resin was neutralized with sodium hydroxide, washed with water, dehydrated and dried to obtain a powdery CPVC. The chlorine content of the obtained CPVC was 68.0% by weight.

Example 2 Preparation and disintegration of PVC were carried out by dehydrating the resin with a centrifugal dehydrator and then pulverizing the resin in a water-containing state (15 parts by weight of water per 100 parts by weight of PVC) without passing through a dryer. Except for this, the procedure was the same as in Example 1.

[Preparation of CPVC] 150 kg of deionized water and 45 kg of PVC obtained above were placed in a glass-lined reaction vessel having an internal volume of 300 liters, and stirred to disperse PVC in water. Then, the reaction vessel was heated. And kept at 70 ° C. Next, nitrogen gas was blown into the reaction tank, and the inside of the tank was replaced with nitrogen gas. Next, chlorine gas is blown into the reaction tank, and while the inside of the tank is irradiated with ultraviolet rays by a mercury lamp, PV gas is applied.
C resin was chlorinated. Continue the chlorination reaction while measuring the hydrochloric acid concentration in the tank and checking the progress of the chlorination reaction,
When the chlorine content of the generated CPVC reached 68.0% by weight, the supply of chlorine gas was stopped, and the chlorination reaction was terminated. Furthermore, nitrogen gas was blown into the tank to remove unreacted chlorine, and after neutralizing the obtained resin with sodium hydroxide,
After washing with water, dehydration and drying, a powdery CPVC resin was obtained. The chlorine content of the obtained CPVC was 68.0% by weight.
Met.

Example 3 Preparation of PVC was carried out except that partially saponified polyvinyl acetate (average degree of saponification: 72 mol% and average degree of polymerization: 700) was 450 ppm and sorbitan monolaurate was 1,800 ppm. It carried out like Example 1. The collapse of PVC was performed in the same manner as in Example 1 except that the rotation speed of the BUSS kneader was set to 80 rpm.
Preparation of CPVC was performed in the same manner as in Example 2.

Example 4 The preparation of PVC was carried out except that partially saponified polyvinyl acetate (average degree of saponification: 72 mol% and average degree of polymerization: 700) was 1,100 ppm and sorbitan monolaurate was 1,200 ppm. Was performed in the same manner as in Example 1. Disintegration of PVC was performed in the same manner as in Example 1.
Preparation of CPVC was performed in the same manner as in Example 1.

Example 5 Preparation of PVC was carried out by changing the kind of partially saponified polyvinyl acetate to (average degree of saponification: 76 mol% and average degree of polymerization: 1,000) to 250 ppm, and converting sorbitan monolaurate to poly (vinyl acetate). The procedure was performed in the same manner as in Example 1 except that oxyethylene alkyl ether sulfate was changed to 40 ppm. Example 1 PVC collapse
The same was done. Preparation of CPVC was performed in the same manner as in Example 1.

(Example 6) [Preparation of PVC] In a polymerization vessel (pressure-resistant autoclave) having an internal volume of 100 liters, 50 kg of deionized water and vinyl chloride monomer were partially saponified polyvinyl acetate (average saponification degree). 88 mol% and an average degree of polymerization of 1,000) to 1,200
After the addition of ppm, 550 ppm of t-butyl peroxy neodecanoate was added. Next, the inside of the polymerization vessel was 45 mm
After degassing to Hg, 33 kg of vinyl chloride monomer was charged and stirring was started.

The polymerization vessel was heated to 57 ° C. to start polymerization,
This temperature was maintained until the end of the polymerization reaction. Polymerization conversion rate is 90
%, The reaction was terminated, and the unreacted monomer in the polymerization vessel was recovered. Then, the polymer was taken out of the system in the form of slurry, and dehydrated and dried to obtain PVC. BE of the obtained PVC
The T specific surface area value was 0.5 m ² / g. The ESCA analysis value indicating the degree of the existence of the skin layer was 0.11. Disintegration of PVC was performed in the same manner as in Example 1. CPV
Preparation of C was performed in the same manner as in Example 1.

(Example 7) [Preparation of PVC] In a polymerization vessel (pressure-resistant autoclave) having an internal volume of 100 liters, partially saponified polyvinyl acetate (average saponification degree) was added to 50 kg of deionized water and vinyl chloride monomer. 72 mol% and an average degree of polymerization of 750) of 1,200 pp
m, t-butyl peroxy neodecanoate 55
0 ppm was added. Next, the inside of the polymerization vessel was 45 mmHg.
After degassing, 33 kg of a vinyl chloride monomer was charged and stirring was started.

The polymerization was started by heating the polymerization vessel to 57 ° C.
This temperature was maintained until the end of the polymerization reaction. Polymerization conversion rate is 90
%, The reaction was terminated, and the unreacted monomer in the polymerization vessel was recovered. Then, the polymer was taken out of the system in the form of slurry, and dehydrated and dried to obtain PVC. BE of the obtained PVC
The T specific surface area value was 0.7 m ² / g. The ESCA analysis value indicating the existence degree of the skin layer was 0.2. Disintegration of PVC was carried out in the same manner as in Example 1 except that the aqueous medium was used and the rotation speed of the BUSS kneader was set to 150 rpm. Preparation of CPVC was performed in the same manner as in Example 1.

Example 8 Preparation of PVC was carried out in the same manner as in Example 4. The collapse of PVC was performed in the same manner as in Example 1 except that the rotation speed of the BUSS co-kneader was 150 rpm. Preparation of CPVC was performed in the same manner as in Example 1.

Example 9 Preparation of PVC was performed in the same manner as in Example 1. Agglomerate diameter was as shown in Table 4.
The measurement of the agglomerate diameter was performed by the following method.

[Preparation of CPVC] 150 kg of deionized water and 45 kg of the above-obtained PVC were charged into a 300-liter glass-lined reaction vessel, and the mixture was stirred to form a PVC.
Was dispersed in water, and then the temperature of the reactor was raised to 110 ° C. Next, nitrogen gas was blown into the reaction tank, and the inside of the tank was replaced with nitrogen gas. Then, chlorine gas was blown into the reaction tank to chlorinate PVC. The chlorination reaction was continued while measuring the hydrochloric acid concentration in the tank to check the progress of the chlorination reaction, and when the chlorine content of the generated CPVC reached 68.0% by weight, the supply of chlorine gas was stopped. Then, the chlorination reaction was completed. Furthermore, nitrogen gas was blown into the tank to remove unreacted chlorine, and the obtained resin was neutralized with sodium hydroxide, washed with water, dehydrated and dried to obtain a powdery CPVC. The chlorine content of the obtained CPVC was 68.0% by weight.
Met.

Example 10 Preparation of PVC was performed in the same manner as in Example 1. Preparation of CPVC was performed in the same manner as in Example 2.

Example 11 Preparation of PVC was carried out except that partially saponified polyvinyl acetate (average degree of saponification: 72 mol% and average degree of polymerization: 700) was 450 ppm and sorbitan monolaurate was 1,800 ppm. It carried out like Example 1. Preparation of CPVC was performed in the same manner as in Example 2.

Example 12 The preparation of PVC was carried out except that the partially saponified polyvinyl acetate (average degree of saponification: 72 mol% and average degree of polymerization: 700) was 1,100 ppm and sorbitan monolaurate was 1,200 ppm. Was performed in the same manner as in Example 1. Preparation of CPVC was performed in the same manner as in Example 9.

Comparative Example 1 Preparation of PVC was performed in the same manner as in Example 1. The collapse of PVC was performed in the same manner as in Example 1 except that the rotation speed of the BUSS kneader was set to 50 rpm. Preparation of CPVC was performed in the same manner as in Example 1.

(Comparative Example 2) Preparation of PVC was performed in the same manner as in Example 2. Disintegration of PVC was performed in the same manner as in Example 2 except that the rotation speed of the BUSS co-kneader was set to 50 rpm. Preparation of CPVC was performed in the same manner as in Example 2.

(Comparative Example 3) Preparation of PVC was performed in the same manner as in Example 3. No PVC disintegration treatment was performed. CPV
Preparation of C was performed in the same manner as in Example 3.

(Comparative Example 4) Preparation of PVC was carried out in the same manner as in Example 5. The collapse of PVC was performed in the same manner as in Example 5 except that the rotation speed of the BUSS co-kneader was set to 80 rpm. Preparation of CPVC was performed in the same manner as in Example 5.

Comparative Example 5 Preparation of PVC was carried out in the same manner as in Example 7, except that the dehydrated resin was dried in a drier. Disintegration of PVC was performed in the same manner as in Example 7, except that a dried resin was used. Preparation of CPVC is described in Example 7.
The same was done.

Comparative Example 6 Preparation of PVC was carried out in the same manner as in Example 4. The collapse of PVC was performed in the same manner as in Example 1 except that the rotation speed of the BUSS kneader was set to 50 rpm. Preparation of CPVC was performed in the same manner as in Example 1.

Comparative Example 7 The preparation of PVC was carried out by changing the kind of partially saponified polyvinyl acetate to 250 ppm by changing the average saponification degree to 76 mol% and the polymerization degree to 1000, and converting sorbitan monolaurate to polyoxyethylene alkyl. The same operation as in Example 1 was carried out except that the concentration was changed to 40 ppm by changing to an ether sulfate salt. Preparation of CPVC is described in Example 9.
The same was done.

Comparative Example 8 Preparation of PVC was carried out in the same manner as in Example 6. Preparation of CPVC was performed in the same manner as in Example 2.

(Comparative Example 9) Preparation of PVC was carried out in the same manner as in Example 7. Preparation of CPVC was performed in the same manner as in Example 1.

The PVC and CPVC obtained in the above Examples and Comparative Examples were subjected to the following performance evaluations, and the results are shown in Tables 1 to 4.

(1) Measurement of BET specific surface area value About 2 g of a measurement sample is put into a sample tube, and 7
After degassing the sample for 3 hours at 0 ° C., the sample weight was measured accurately. The sample after the pretreatment was attached to a measuring section (40 ° C. constant temperature bath) to start measurement. After the measurement, a BET plot was performed from the data on the adsorption side of the adsorption isotherm to calculate the specific surface area. Note that a specific surface measurement device “BELSORP 28SA” (manufactured by Bell Japan Co., Ltd.) was used as a measurement device, and nitrogen gas was used as a measurement gas.

(2) ESCA Analysis The surface of the PVC particles was measured using ESCA (Electron Sp
electroscopyfor Chemical An
analysis (electron spectrochemical analysis) and C1S
From the peak areas of (carbon), Cl1s (chlorine), and O1s (oxygen), the vinyl chloride resin component on the particle surface was quantitatively analyzed based on the chlorine amount. -Equipment used: "JPS-90FX" manufactured by JEOL Ltd.-Usage conditions: X-ray source (Mg Kα ray), 12kV-15
mA Scan speed: 200 ms / 0.1 eV / scan Path energy: 30 eV

(3) Measurement of Volume Average Particle Diameter The collapsed and crushed PVC particles were immersed in acetone for 24 hours, and then measured in distilled water using a particle size distribution analyzer LA910 (manufactured by Horiba, Ltd.).

(4) Judgment of pulverization into agglomerates In order to check whether the collapsed and pulverized PVC particles are pulverized to agglomerates, first, the PVC particles before collapse and pulverization are cooled with liquid nitrogen. The particles are cut with a razor, and the obtained particles are observed with a scanning electron microscope (SEM) to confirm the size of agglomerates. Thereafter, the disintegrated and pulverized PVC particles are similarly observed, and SEM photographs are taken. The particles in the obtained SEM photograph that are smaller than the size of the agglomerate and the other particles are each traced on a transparent sheet, and the respective areas are calculated using an image analyzer (manufactured by Pierce). From the obtained area, the agglomerate occupation area ratio was calculated according to the following equation, and the value was 95
% Or more, it is determined that the PVC particles have been refined to agglomerates. {Ad / (Ad + Au)} × 100 [where, Ad: particle area equal to or less than agglomerate, Au:
The particle areas other than those on the left are respectively shown. (5) Measurement of agglomerate diameter The PVC particles before disintegration and pulverization were appropriately encapsulated in a gelatin capsule together with an acrylic monomer, and allowed to stand at room temperature for 24 hours to polymerize the acrylic monomer. After that, the capsule was placed in an ultramicrotome (LKB Instrument).
nts), cut into a thickness of about 90 nm to prepare an ultrathin section, placed on a grid mesh, and observed with a transmission electron microscope JEM-1010 (manufactured by JEOL Ltd.). The magnification was 5000 times.

(6) Processability (Measurement of Gelation Temperature) Using “Rheocord 90” manufactured by Haake, 55 g of the following resin composition was heated at a rotational speed of 40 rpm and a temperature of 150 ° C.
Kneading was carried out while increasing the temperature at a rate of 5 ° C./min from the temperature, and the temperature at which the kneading torque was maximized was measured. In addition, as a resin composition, with respect to 100 parts by weight of CPVC resin,
A material consisting of 3 parts by weight of tribasic lead sulfate, 1 part by weight of dibasic lead stearate and 10 parts by weight of MBS resin was used.

(7) Thermal Stability Test The above resin composition was supplied to a kneader comprising two 8-inch rolls and kneaded at a roll surface temperature of 205 ° C., and the kneaded material was wound around a roll every 30 seconds. Wound CPVC
While turning over the resin sheet, a small amount of the sheet was cut out every minute, the degree of coloring of the sheet was compared, and the thermal stability was determined by the time when the sheet turned black-brown.

(8) Vicat softening temperature A 5 mm thick CPVC resin sheet prepared in the above thermal stability test was cut into 15 mm squares to obtain a measurement sample.
It measured based on J1SK7206 (weight 1.0kgf).

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

[0083]

The CPVC of the present invention focuses on the surface state and the internal state of PVC, controls the agglomerate diameter, which is an aggregate of primary particles, refines the PVC obtained therefrom, and then chlorinates it. It has excellent gelling performance and heat resistance. In addition, the obtained PVC is not dried, but is dispersed in an aqueous medium as it is and chlorinated, thereby preventing gelation and omitting or simplifying the drying step of the PVC, thereby reducing energy consumption. Manufacturing efficiency can also be improved.

(72) Inventor Yoshihiko Eguchi 4560 Kaiseicho, Shinnanyo-shi, Yamaguchi Prefecture Sekisui Chemical Co., Ltd.

Claims (5)

[Claims] Claims: 1. A chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin, wherein the vinyl chloride resin is disintegrated or pulverized to a volume average particle size of 0.5 to 50 μm, A chlorinated vinyl chloride resin characterized by being chlorinated. 2. A chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin, wherein the vinyl chloride resin is disintegrated or pulverized to a size corresponding to agglomerate particles, which are aggregates of primary particles. Chlorinated vinyl chloride resin characterized by being chlorinated. 3. A chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin, wherein the vinyl chloride resin comprises:
The BET specific surface area value is 1.3 to 8 m ² / g, and in the particle surface analysis by electron spectrochemical analysis, the peak ratio [(chlorine atom peak) at 1S bond energy value (eV) between carbon atom and chlorine atom] × 2 / carbon atom peak]
Is greater than 0.6. The chlorinated vinyl chloride resin according to claim 1 or 2, wherein 4. A chlorinated vinyl chloride resin obtained by chlorinating a vinyl chloride resin, wherein the vinyl chloride resin comprises:
The BET specific surface area value is 1.3 to 8 m ² / g, and in the particle surface analysis by electron spectrochemical analysis, the peak ratio [(chlorine atom peak) at 1S bond energy value (eV) between carbon atom and chlorine atom] × 2 / carbon atom peak]
Is greater than 0.6, and the agglomerate diameter, which is an aggregate of primary particles of the vinyl chloride resin, is 1
A chlorinated vinyl chloride resin characterized by chlorinating a resin having a diameter of from 7 to 7 μm. 5. A method comprising disintegrating or pulverizing a vinyl chloride resin together with an aqueous medium to a volume average particle diameter of 0.5 to 50 μm, and chlorinating the vinyl chloride resin. 5. The method for producing a chlorinated vinyl chloride resin according to any one of 1 to 4.