KR20130090733A - Method of preparing vinyl chloride latex having high efficiency - Google Patents

Method of preparing vinyl chloride latex having high efficiency Download PDF

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Publication number
KR20130090733A
KR20130090733A KR1020120091605A KR20120091605A KR20130090733A KR 20130090733 A KR20130090733 A KR 20130090733A KR 1020120091605 A KR1020120091605 A KR 1020120091605A KR 20120091605 A KR20120091605 A KR 20120091605A KR 20130090733 A KR20130090733 A KR 20130090733A
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South Korea
Prior art keywords
vinyl chloride
producing
latex
monomer
based latex
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KR1020120091605A
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Korean (ko)
Inventor
이현섭
육경석
김한홍
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주식회사 엘지화학
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Publication of KR20130090733A publication Critical patent/KR20130090733A/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F114/02—Monomers containing chlorine
    • C08F114/04—Monomers containing two carbon atoms
    • C08F114/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/001—Removal of residual monomers by physical means
    • C08F6/003—Removal of residual monomers by physical means from polymer solutions, suspensions, dispersions or emulsions without recovery of the polymer therefrom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F6/00—Post-polymerisation treatments
    • C08F6/006—Removal of residual monomers by chemical reaction, e.g. scavenging
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

The present invention provides a swelling promotion step in which a polymerization water, a vinyl chloride monomer, an emulsifier, and a monomer absorption promoter are introduced into a pre-mixing tank and stirred to obtain a mixture, a homogenization step of passing the mixture through a rotary homogenizer, and the homogenized mixture is a reactor. By including a polymerization step of polymerization in, it is possible to prepare a vinyl chloride-based latex particles having various sizes and to increase the stability of the resulting droplets.

Description

Method of preparing vinyl chloride latex having high efficiency

The present invention relates to a method for producing a vinyl chloride-based latex, and more particularly, a swelling promoting step of adding a polymerization water, a vinyl chloride monomer, an emulsifier and a monomer absorption accelerator to a pre-mixing tank and stirring to obtain a mixture. By including a homogenization step of passing through a rotary homogenizer and a polymerization step of polymerizing the homogenized mixture in a reactor, particles having various sizes can be produced and a method of producing vinyl chloride latex can improve stability of the resulting droplets. It is about.

The preparation of the paste vinyl chloride resin by the seed emulsion polymerization method involves the introduction of seeds having two average particle diameters different from each other at the initial stage of polymerization, whereby the vinyl chloride monomer is reacted with the seeds to produce the final latex particles. Among the two kinds of seeds, the first seed is prepared by adding a vinyl chloride monomer, an emulsifier, a oil-soluble initiator, etc., homogenizing using a homogenizer pump, and then polymerizing. The second seed is prepared by emulsion polymerization. Since the first seed contains the oil-soluble initiator in the particle, it has a reaction site by itself. Therefore, it is necessary to add an excessive amount of the initiator during the first seed polymerization to leave an appropriate amount of the initiator content in the particles in which the polymerization is completed so that the polymerization start is well activated during the seed emulsion polymerization. In the method of preparing the first seed, there is a problem in that the control of the particle size through changing the amount of the emulsifier is limited and sometimes droplets are not produced or the stability is inferior.

An object of the present invention to solve the problems of the prior art as described above is a monomer absorption in the method of manufacturing the first seed is limited in the control of the particle size by changing the amount of the emulsifier input and sometimes there is a problem that drops are not generated or stability is poor The introduction of the accelerator and the step of promoting the swelling are to be solved.

The above object of the present invention can be achieved by the present invention described below.

According to the present invention, a swelling promoting step of adding a polymerization water, a vinyl chloride monomer, an emulsifier and a monomer absorption promoter into a pre-mixing tank and stirring to obtain a mixture; Homogenization step of passing the mixture through a rotary homogenizer; And a polymerization step of polymerizing the homogenized mixture in a reactor.

The present invention can produce particles of various sizes according to the desired physical properties and applications, it is easy to achieve the desired physical properties when applied to the seed emulsion polymerization. In addition, the reaction time can be shortened.

In addition, the present invention can produce a wide range of particles by using a homogenizer in the homogenization method, and increase the stability of droplets generated by adding a swelling promotion process together with a monomer absorption promoter.

1 is a view showing a manufacturing process of the vinyl chloride-based latex according to an embodiment of the present invention.

According to the present invention, a swelling promotion step of adding a polymerization water, a vinyl chloride monomer, an emulsifier and a monomer absorption accelerator into a pre-mixing tank and stirring to obtain a mixture; Homogenization step of passing the mixture through a rotary homogenizer; And a polymerization step of polymerizing the homogenized mixture in a reactor.

Hereinafter, the present invention will be described in detail.

The present invention adjusts the rotational speed of the rotary homogenizer to produce particles. Firstly, the monomer absorption promoter, the subsidiary material and the monomer are added to the pre-mixing tank, followed by stirring for a predetermined time in a vacuum state. The rotary homogenizer can then be passed to form a droplet and then polymerized to produce a seed of the desired size. At this time, in order to make particles of a desired size, particles of a desired particle size are manufactured by controlling the number of cycles in the homogenization process and adjusting the rotor stator gap. Swelling is a process in which the fat-soluble monomer absorption accelerator is sufficiently stirred for about 5 to 60 minutes under a pressure of about 0.1 to 5 kg / cm 2 before passing through the homogenizer. The latex produced through this method is highly stable in droplets and can produce particles of a size that was difficult to obtain stably with conventional emulsion control methods. In addition, when the seed emulsion polymerization is carried out using the thus prepared seeds, the polymerization time may be shortened by about 30 minutes or more.

20 to 150 parts by weight of the polymerized water, 0.1 to 10 parts by weight of the emulsifier and 0.1 to 10 parts by weight of the monomer absorption accelerator are added based on 100 parts by weight of the vinyl chloride monomer.

The monomer absorption promoter may use an aliphatic higher alcohol.

The emulsifier is sodium lauryl sulfate (SLS), sodium dodecyl benzene sulfonate (SDBS), sodium dodecyl alkylsulfate (SDS), ammonium lauryl sulfate sulfate, ALS), sodium cetyl stearyl sulfate, sodium lauryl ether sulfate (SLES) and succinate, but may be selected from the group consisting of Uses sodium dodecyl benzene sulfonate, but is not limited thereto.

The swelling promotion step is performed by stirring for 5 to 60 minutes under 0.1 to 5kg / cm 2 pressure.

In addition, the number of cycles of the rotary homogenizer in the homogenizing step may be 10 to 150 times, specifically 20 to 85 times.

In addition, the rotor stator interval may be 0.05 to 10 mm, specifically 0.1 to 1 mm.

Cycling too few times can result in a somewhat larger particle size and a somewhat wider distribution. Cycling too many times can lead to time-consuming and too narrow distribution of particles. The narrower the spacing, the smaller the particle size. Too wide the spacing can make it difficult to obtain uniform particles and reduce stability.

And the present invention provides a vinyl chloride-based latex prepared by the method for producing a vinyl chloride-based latex.

In addition, the present invention provides a method for producing a powdery paste vinyl chloride resin which is subjected to seed emulsion polymerization using the above-described vinyl chloride-based latex as a seed and dried to produce a powdery paste vinyl chloride resin.

It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the scope and spirit of the invention as disclosed in the accompanying claims. Changes and modifications may fall within the scope of the appended claims.

[Example]

Example  One

In a 200 L high-pressure reactor, deionized water 105phm, lauryl peroxide 1.7phm, paraquinone 0.003phm, aliphatic higher alcohol 1phm was added as a monomer absorption accelerator, and vacuum was applied to the reactor at -730mmHg, followed by 100phm of vinyl chloride monomer and sodium 1.6phm of dodecyl benzene sulfonate was added and stirred for 20 minutes at a pressure of 3kg / cm 2 .

After 40-circulation at 0.5 mm intervals using a rotor-stator type homogenizer. Upon completion of homogenization, the reactor temperature was adjusted to 40 ° C. and polymerization was performed.

Example  2

A vinyl chloride-based latex and a powdery paste vinyl chloride resin were prepared in the same manner as in Example 1 except that the number of cycles of the rotor-stator was 80.

Example  3

A vinyl chloride-based latex and a powdery paste vinyl chloride resin were prepared in the same manner as in Example 1 except that the number of cycles of the rotor-stator was 20.

Example  4

Vinyl chloride-based latex and powdery paste vinyl chloride resin were prepared in the same manner as in Example 1 except that the rotor-stator spacing was 0.3 mm.

Comparative example  One

A vinyl chloride latex and a powdery paste vinyl chloride resin were prepared in the same manner as in Example 1 except that the swelling promotion step was not performed.

Comparative example  One

A vinyl chloride-based latex and a powdery paste vinyl chloride resin were prepared in the same manner as in Example 1 except that the emulsifier input amount was 0.4 phm without performing the swelling promotion step.

Comparative example  3

A vinyl chloride latex and a powdery paste vinyl chloride resin were prepared in the same manner as in Example 1 except that the rotor-stator gap was adjusted to 1.5 mm without performing the swelling promotion process.

[Test Example]

The average particle diameter and scale amount of the vinyl chloride polymer prepared in Examples and Comparative Examples were measured as follows.

* Average particle size: The particle size of the prepared vinyl chloride latex was measured using a Microtrac nanotrac150.

Scale amount: The weight of the material applied to the strainer after polymerization was measured approximately.

Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Cycle count 40 80 20 40 40 40 40 Swelling Promotion Process practice practice practice practice Absenteeism Absenteeism Absenteeism Rotor-stator spacing (mm) 0.5 0.5 0.5 0.3 0.5 0.5 1.5 Emulsifier amount (phm) 0.8 0.8 0.8 0.8 0.8 0.4 0.8 Particle size (탆) 0.65 0.42 0.91 0.58 0.68 - - scale Less than 100g Less than 100g Less than 100g Less than 100g 780 g Cohesion Cohesion

As shown in Table 1, when comparing Examples 1 to 4 with Comparative Examples 1 to 3, which are not subjected to the swelling promotion process, the scale does not occur much, so the stability of the droplets is high and the existing emulsifier control method is stable. It was able to produce particles of a size that was difficult to obtain.

Claims (8)

A swelling promoting step of introducing the polymerized water, the vinyl chloride monomer, the emulsifier and the monomer absorption promoter into the pre-mixing tank and stirring to obtain a mixture;
Homogenization step of passing the mixture through a rotary homogenizer; And
A polymerization step of polymerizing the homogenized mixture in a reactor;
Method for producing a vinyl chloride-based latex comprising a. The method of claim 1,
20 to 150 parts by weight of the polymerized water, 0.1 to 10 parts by weight of the emulsifier and 0.1 to 10 parts by weight of the monomer absorption accelerator, are prepared based on 100 parts by weight of the vinyl chloride monomer. Way. The method of claim 1,
The monomer absorption promoter is a method of producing a vinyl chloride-based latex, characterized in that the aliphatic higher alcohol. The method of claim 1,
The emulsifier is sodium lauryl sulfate (SLS), sodium dodecyl benzene sulfonate (SDBS), sodium dodecyl alkylsulfate (SDS), ammonium lauryl sulfate sulfate, ALS), sodium cetyl stearyl sulfate, sodium lauryl ether sulfate (SLES) and succinate, characterized in that at least one selected from the group consisting of Method for producing vinyl latex. The method of claim 1,
The swelling promoting step is a method for producing a vinyl chloride-based latex, characterized in that for 5 to 60 minutes stirring under a pressure of 0.1 to 5kg / cm 2 . The method of claim 1,
Method for producing a vinyl chloride-based latex, characterized in that the number of cycles of the rotary homogenizer in the homogenizing step is 10 to 150 times, the rotor-stator interval is 0.05 to 10mm. Vinyl chloride-based latex prepared by the method for producing a vinyl chloride-based latex according to claim 1. A method of producing a powdery paste vinyl chloride resin, wherein the seed emulsion polymerization is carried out using the vinyl chloride latex according to claim 7 and dried to prepare a powdery paste vinyl chloride resin.
KR1020120091605A 2012-02-06 2012-08-22 Method of preparing vinyl chloride latex having high efficiency KR20130090733A (en)

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KR20120011621 2012-02-06
KR1020120011621 2012-02-06

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