KR102118075B1 - Vinyl chloride polymer, method for preparing the same and vinyl chloride polymer composition - Google Patents

Abstract

The present invention relates to a vinyl chloride-based polymer, a method for producing the same, and a vinyl chloride-based polymer composition comprising the same, more specifically, containing a higher fatty acid having 10 to 18 carbon atoms, and having an average particle diameter of 0.24 μm to 2.0 μm. The higher fatty acid relates to a vinyl chloride-based polymer, a preparation method thereof, and a vinyl chloride-based polymer composition comprising the same, which is contained in an amount of more than 0 parts by weight to 5 parts by weight or less based on 100 parts by weight of the vinyl chloride-based polymer.

Description

VINYL CHLORIDE POLYMER, METHOD FOR PREPARING THE SAME AND VINYL CHLORIDE POLYMER COMPOSITION

The present invention relates to a vinyl chloride-based polymer, and more particularly, to a vinyl chloride-based polymer having excellent viscosity stability.

Vinyl chloride-based polymer is a polymer containing 50% by weight or more of repeating units derived from vinyl chloride monomer (VCM), which is inexpensive, easy to control hardness, and can be applied to most processing equipment. Is diverse. In addition, it is widely used in various fields because it can provide a molded article excellent in physical and chemical properties, such as mechanical strength, weather resistance, and chemical resistance.

These vinyl chloride polymers are produced in different forms depending on the application. For example, vinyl chloride-based polymers for straight processing such as extrusion, calendering, and injection processes are generally prepared by suspension polymerization, and vinyl chloride-based polymers for paste processing such as dipping, spraying, and coating are prepared by emulsion polymerization.

The paste processing is generally performed by spray drying the vinyl chloride-based polymer latex for paste processing obtained by emulsion polymerization to form final resin particles, and the particles are dispersed in a solvent or a plasticizer for coating (reverse roll-coating, knife). Flooring, wallpaper, tarpaulin, raincoat, through processes such as coating, screen coating, spray coating, gravure and csreen printing, ratotion casting, shell casting and dipping, It is applied to products such as gloves, automotive underbody coatings, sealants and carpet tiles.

These vinyl chloride-based polymers for paste processing are difficult to apply alone, and are usually used in a form of plastisol composed of various additives such as a heat stabilizer together with a plasticizer, and in order to improve processability, the plastic It is important to keep the flowability low by lowering the viscosity of the stizol.

On the other hand, the vinyl chloride-based polymer for paste processing is usually stored for a long period of time after production in a bag or a flacon bag. Due to the residual emulsifier contained in the polymer, it is initially produced according to the storage environment such as humidity or storage period in the atmosphere. There is a problem that the viscosity of the polymer is changed.

JP 1998-036407 A

The present invention has been devised to solve the problems of the prior art, and has an object to provide a vinyl chloride-based polymer having excellent viscosity stability, a manufacturing method thereof, and a vinyl chloride-based polymer composition comprising the same.

According to an embodiment of the present invention for solving the above problems, the present invention includes a higher fatty acid having 10 to 18 carbon atoms, the average particle diameter is 0.24 ㎛ to 2.0 ㎛, the higher fatty acid is 100% by weight of a vinyl chloride polymer It provides a vinyl chloride-based polymer that is contained in an amount of more than 0 parts by weight to 5 parts by weight or less based on parts.

In addition, the present invention comprises the steps of preparing a vinyl chloride-based polymer latex comprising a vinyl chloride-based polymer having an average particle diameter of 0.24 ㎛ to 2.0 ㎛ (S1); Step of introducing and stirring a higher fatty acid having 10 to 18 carbon atoms in the prepared vinyl chloride-based polymer latex (S2); And drying the stirred vinyl chloride polymer latex to obtain a vinyl chloride polymer powder (S3), wherein the higher fatty acid is greater than 0 parts by weight to less than 5 parts by weight based on 100 parts by weight of the vinyl chloride polymer. It provides a method for producing a vinyl chloride-based polymer that is added as the content of.

According to the present invention, when a vinyl chloride-based polymer or a plastisol containing the same is prepared and stored for a long period of time, the viscosity stability is excellent, and thus the processability and physical properties of the initial polymer and the vinyl chloride-based polymer or a plastisol containing the same after long-term storage are excellent. It has the effect of preventing degradation.

Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.

Terms or words used in the description and claims of the present invention should not be construed as being limited to ordinary or lexical meanings, and the inventor appropriately explains the concept of terms in order to explain his or her invention in the best way. Based on the principle of being able to be defined, it should be interpreted as meaning and concept consistent with the technical idea of the present invention.

The vinyl chloride-based polymer according to the present invention includes a higher fatty acid having 10 to 18 carbon atoms, and the average particle diameter of the vinyl chloride-based polymer is 0.24 μm to 2.0 μm, and the higher fatty acid is based on 100 parts by weight of the vinyl chloride-based polymer. It may be included in an amount of more than 0 parts by weight to 5 parts by weight or less.

The vinyl chloride-based polymer according to an embodiment of the present invention may include 50 to 100% by weight of repeat units derived from vinyl chloride monomer and 0 to 50% by weight of repeat units derived from vinyl monomer. The vinyl chloride monomer-derived repeating unit may mean a repeating unit formed through polymerization reaction of a vinyl chloride monomer (VCM), and the vinyl-based monomer-derived repeating unit is a vinyl-based monomer copolymerizable with the vinyl chloride monomer. It may mean a repeating unit formed through a polymerization reaction with a vinyl chloride monomer. The vinyl monomers include, for example, olefin compounds such as ethylene and propylene; Vinyl esters such as vinyl acetate and vinyl propionate, and unsaturated nitriles such as acrylonitrile; Vinyl alkyl ethers such as vinyl methyl ether and vinyl ethyl ether; And unsaturated fatty acids such as acrylic acid, methacrylic acid, itaconic acid and maleic acid, and anhydrides of these fatty acids.

The vinyl chloride-based polymer according to the present invention may be, for example, a paste vinyl chloride-based polymer, and the average particle diameter of the vinyl chloride-based polymer is, for example, 0.24 μm to 2.0 μm, 0.5 μm to 1.5 μm, or 1.0 μm to It may be 1.5 ㎛, excellent in viscosity stability within this range, there is an effect of excellent workability even after long-term storage.

According to an embodiment of the present invention, the higher fatty acid contained in the vinyl chloride-based polymer may be included in a mixed state on a three-dimensional network of the vinyl chloride-based polymer. That is, on the 3D network in which the main chain of the vinyl chloride polymer is entangled with each other, the higher fatty acids may be present in a mixed state.

The higher fatty acid according to the present invention may include, for example, one or more functional groups or bonds selected from the group consisting of one or more hydroxy groups, one or more unsaturated bonds, and two or more carboxyl groups. As a specific example, the higher fatty acid may include a higher fatty acid having 10 to 18 carbon atoms containing one hydroxy group, a higher fatty acid having 10 to 18 carbon atoms including one unsaturated bond, and 10 to 10 carbon atoms including one hydroxy group and one unsaturated bond. Higher fatty acids of 18, higher fatty acids having 10 to 18 carbon atoms containing two unsaturated bonds, and higher fatty acids having 10 to 18 carbon atoms having both carboxyl groups at both ends of the carbon chain. Here, the unsaturated bond may mean a double bond or a triple bond between carbon and carbon.

The higher fatty acid according to an embodiment of the present invention may be at least one selected from the group consisting of castor oil fatty acid, dehydrated castor oil fatty acid, hardened castor oil fatty acid, sebacic acid and undecylenic acid, and in this case, viscosity It has an excellent stability effect.

The higher fatty acid according to an embodiment of the present invention may be a saponified higher fatty acid. The saponified higher fatty acid may refer to a higher fatty acid saponification of higher fatty acids with a saponification agent. The saponifier may be, for example, alkali hydroxide.

The higher fatty acid is, for example, greater than 0 parts by weight to less than 5 parts by weight, 0.01 parts by weight to 4 parts by weight, 0.05 parts by weight to 3 parts by weight, or 0.05 parts by weight to 1 part by weight based on 100 parts by weight of the vinyl chloride polymer. It can be included, while preventing the mechanical property degradation of the vinyl chloride-based polymer, there is an effect of excellent viscosity stability.

The vinyl chloride-based polymer according to an embodiment of the present invention may be a vinyl chloride-based polymer for paste processing.

As another example, the polymerization degree of the vinyl chloride-based polymer may be 500 to 2,000, 800 to 1,500, or 1,000 to 1,500.

The method for producing a vinyl chloride-based polymer of the present invention comprises the steps of preparing a vinyl chloride-based polymer latex comprising a vinyl chloride-based polymer having an average particle diameter of 0.24 μm to 2.0 μm (S1); Step of introducing and stirring a higher fatty acid having 10 to 18 carbon atoms in the prepared vinyl chloride-based polymer latex (S2); And drying the stirred vinyl chloride polymer latex to obtain a vinyl chloride polymer powder (S3), wherein the higher fatty acid is 0 parts by weight based on 100 parts by weight of the vinyl chloride polymer (based on solids). It may be added in an amount of more than 5 parts by weight. According to the above production method, it is possible to produce a vinyl chloride-based polymer having a higher fatty acid having 10 to 18 carbon atoms and an average particle diameter of the vinyl chloride-based polymer of 0.24 μm to 2.0 μm according to the present invention.

The production of the vinyl chloride-based polymer latex in the step (S1) may be carried out by an emulsion polymerization method, a fine suspension polymerization method, a suspension polymerization method or a bulk polymerization method, preferably an emulsion polymerization method, a fine suspension polymerization method or a suspension. It can be carried out by a polymerization method, in this case has the effect of excellent viscosity stability of the vinyl chloride-based polymer prepared.

The emulsion polymerization may be carried out by, for example, adding and reacting a vinyl chloride monomer and a water-soluble polymerization initiator in a vacuum reactor filled with a first emulsifier, and additionally adding a second emulsifier separately from the first emulsifier during polymerization. The second emulsifier may be continuously added during polymerization.

Here, the reactor in which the first emulsifier is filled may indicate a reactor in which the first emulsifier is contained, and if necessary, additives such as polymerization water, a dispersant, a reaction inhibitor, an electrolyte, and a molecular weight modifier are additionally filled in addition to the first emulsifier. It may be. At this time, with respect to 100 parts by weight of the vinyl chloride monomer, the first emulsifier is 0.02 parts by weight to 0.4 parts by weight, the water-soluble polymerization initiator is 0.01 parts by weight to 2 parts by weight, the second emulsifier is 0.01 parts by weight to 6 parts by weight, and the polymerization water is 70 parts by weight to 125 parts by weight, the electrolyte is 0.0001 parts by weight to 3 parts by weight, the molecular weight modifier may be used as 0.01 parts by weight to 2 parts by weight.

The first emulsifier and the second emulsifier may each be the same or different, and specifically, the first emulsifier and the second emulsifier are sodium lauryl sulfate, lauryl benzene sulfonic acid, alpha-olefin sulfonate, and sodium lauryl ethoxy, respectively. Rated sulfate, sodium octadecyl sulfate, sodium lauryl ether sulfate, and one or more selected from the group consisting of straight chain alkylbenzene sulfonates, wherein the water-soluble polymerization initiator is, for example, a group consisting of potassium persulfate, ammonium persulfate and hydrogen peroxide. It may be one or more selected from, and the molecular weight modifier may be, for example, n-butyl mercaptan, n-octyl mercaptan, n-dodecylmercaptan, t-dodecylmercaptan, etc., and the electrolyte is potassium chloride, sodium chloride as an example. , One or more selected from the group consisting of potassium bicarbonate, sodium carbonate, potassium carbonate, potassium hydrogen sulfite, sodium hydrogen sulfite, potassium potassium pyrophosphate, sodium pyrophosphate, tripotassium phosphate, trisodium phosphate, dipotassium hydrogen phosphate and disodium hydrogen phosphate Can be. The emulsion polymerization may be carried out in the temperature range of 30 ℃ to 70 ℃ as an example.

According to an embodiment of the present invention, the method for preparing the vinyl chloride-based polymer may include the step of saponifying the higher fatty acid with a saponifying agent prior to the introduction of the higher fatty acid in step (S2). The saponifier may be, for example, alkali hydroxide, and as a specific example, sodium hydroxide or potassium hydroxide. As another example, the saponifier may be used in a molar ratio of 0.1 mol to 5 mol, 0.5 mol to 3 mol, or 1 mol to 1.5 mol with respect to 1 mol of the higher fatty acid.

The method for preparing the vinyl chloride-based polymer may further include a dehydration and washing step before drying after stirring in the step (S3), for example.

Meanwhile, according to the present invention, a vinyl chloride-based polymer composition comprising the vinyl chloride-based polymer and a plasticizer is provided.

The plasticizer may be an organic additive material that improves molding processability at a high temperature of the vinyl chloride polymer by increasing the thermoplasticity of the polymer by forming a plastisol together with the vinyl chloride polymer, and specifically, the plasticizer is a phosphoric acid ester -Based plasticizer, aliphatic dibasic acid ester-based plasticizer, epoxy-based plasticizer and polyester-based plasticizer may be at least one selected from the group consisting of, and more specifically, the plasticizer is dibutylphthalate (DBP), di-2-ethylhexyl phthalate (DOP), phthalic acid ester plasticizers such as diisodecyl phthalate (DIDP), trimellitic acid ester plasticizers such as trioctyl trimellitate (TOTM), tridecyl trimellitate, tricresyl phosphate, trioctyl phosphate, etc. It may be at least one selected from the group consisting of aliphatic dibasic acid ester plasticizers such as phosphate ester plasticizer, dioctyl adipate, diisodecyl adipate, epoxy plasticizer and polyester plasticizer.

According to an embodiment of the present invention, the plasticizer may be included in 1 to 200 parts by weight, 30 to 150 parts by weight, or 50 to 150 parts by weight based on 100 parts by weight of the vinyl chloride polymer, and processability and Productivity is excellent.

The vinyl chloride-based polymer composition may be, for example, plastisol, and the plastisol may represent a mixture of a vinyl chloride-based polymer and a plasticizer so that it can be processed into a molded, molded, or continuous film by heating, Another example may be a paste.

The vinyl chloride-based polymer composition according to an embodiment of the present invention may have an initial viscosity greater than 18,200 cP to 25,000 cp or less, 18,500 cP to 24,000 cP, or 19,000 cP to 22,000 cP, and have excellent processability within this range. There is.

In addition, the vinyl chloride-based polymer composition according to an embodiment of the present invention may have an initial viscosity and a rate of change in viscosity over time after 3 months of less than 1.56, 0.5 to 1.5, or 1.0 to 1.25, and have viscosity stability within this range. It has an excellent effect.

Hereinafter, the present invention will be described in more detail by examples. However, the following examples are only intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Example

Example 1

1) Preparation of the first seed

73 kg of deionized water, 1.21 kg of lauryl peroxide, and 0.9 g of paraquinone were added to a 200 L high wax reactor, and vacuum was applied to the reactor at -730 mmHg. To the reactor in a vacuum state, 66 kg of vinyl chloride monomer (VCM) and 7.8 kg of sodium lauryl sulfate were added as an emulsifier and stirred for 15 minutes. Subsequently, the internal temperature of the reactor was lowered to 20° C. or lower, and homogenization was performed for 2 hours using a rotor-stator type homogenizer. After the homogenization was completed, the internal temperature of the reactor was raised to 42° C. and polymerization was carried out. When the pressure in the reactor reached 3.5 kg/cm ² after 558 minutes, the reaction was terminated and unreacted vinyl chloride monomer was recovered and removed to obtain a first seed latex having an average particle diameter of 0.68 μm.

2) Preparation of the second seed

In a 500 L high-pressure reactor, 230 kg of polymerized water, 790 g of lauric acid and 240 g of sodium hydroxide as primary emulsifiers, and 110 g of potassium peroxynate as a water-soluble initiator were added and the reactor was vacuumed while stirring. After adding 185 kg of vinyl chloride monomer (VCM) to the reactor in a vacuum state, the temperature of the reactor was raised to 56°C to perform polymerization. After initiating the polymerization reaction, 11.1 kg of sodium dodecyl benzene sulfonate as a secondary emulsifier was continuously charged into the reactor for 5 hours. Thereafter, when the pressure of the reactor reached 4 kg/cm ² , the reaction was terminated, and unreacted vinyl chloride monomer was recovered and removed to obtain a second seed latex having an average particle diameter of 0.12 μm.

3) Preparation of vinyl chloride polymer

150 kg of deionized water, 15 kg of the first seed, and 6 kg of the second seed were added to a 500 L high-pressure reactor and vacuum was applied to the reactor while stirring. After adding 215 kg of vinyl chloride monomer (VCM) to the reactor in a vacuum state, the reactor temperature was raised to 58°C to perform seed emulsion polymerization. After initiating the polymerization reaction, 1.5 kg of sodium dodecyl benzene sulfonate was continuously added to the reactor as an emulsifier. When the pressure of the reactor reached 4 kg/cm ² after 300 minutes, the reaction was terminated, and unreacted vinyl chloride monomer was recovered and removed to prepare a vinyl chloride polymer latex. At this time, the polymerization degree of the vinyl chloride-based polymer present in the dispersed phase on the vinyl chloride-based polymer latex was 1,200, and the average particle diameter was 1.2 μm.

Castor oil fatty acid saponified in the prepared vinyl chloride-based polymer latex was added to 0.1 parts by weight based on 100 parts by weight of the vinyl chloride-based polymer (based on solid content) and stirred for 30 minutes. Subsequently, the stirred vinyl chloride-based polymer latex was spray dried to prepare a vinyl chloride-based polymer on a powder.

Meanwhile, the average particle diameter of the vinyl chloride-based polymer was measured by diluting the polymer obtained after polymerization to 0.1% by weight in deionized water, and then using a particle size analyzer (Microtrac's Nanotrac150).

Example 2

It was carried out in the same manner as in Example 1, except that the same amount of dehydrated castor oil fatty acid, which was saponified in place of the castor oil fatty acid, which was saponified in Example 1, was added.

Example 3

It was carried out in the same manner as in Example 1, except that the same amount of the cured castor oil fatty acid that was saponified instead of the castor oil fatty acid that was saponified in Example 1 was added.

Example 4

It was carried out in the same manner as in Example 1, except that the same amount of sebacic acid, which was saponified in place of the castor oil fatty acid that was saponified in Example 1, was added.

Example 5

It was carried out in the same manner as in Example 1, except that the same amount of undecylenic acid that was saponified instead of the castor oil fatty acid that was saponified in Example 1 was added.

Comparative Example 1

The same method as in Example 1, except that the vinyl chloride-based polymer latex was not added to the vinyl chloride-based polymer latex, and the vinyl chloride-based polymer latex was spray dried to prepare a vinyl chloride-based polymer on powder. Was carried out.

Experimental Example

In order to measure the viscosity stability of the vinyl chloride-based polymer prepared in Examples and Comparative Examples, 100 parts by weight of the vinyl chloride-based polymer on the obtained powder and 60 parts by weight of dioctylphthalate (DOP) as a plasticizer were mixed to form vinyl chloride. After preparing the system polymer composition, it was stirred for 10 minutes at 800 rpm using a WERKE mixer from EUROSTAR to prepare a plastisol.

Subsequently, an initial viscosity (cP) of the plastisol was measured under a Peltier plate, a 40 mm parallel plate, and a Gap size of 500 μm using a Rotational Rheometer AR2000EX manufactured by TA Instrument. Thereafter, the plastisol was stored at a storage temperature of 25°C and a storage humidity of 70%, and the time-lapse viscosity (cP) after 1 month and 3 months were respectively measured, and the time-lapse rate was calculated according to Equation 1 below. It is shown together in Table 1. At this time, as the aging rate approaches 1, it means that the viscosity stability is excellent.

[Equation 1]

division Example Comparative example One 2 3 4 5 One Average particle diameter (㎛) 1.2 1.2 1.2 1.2 1.2 1.2 Initial viscosity (right after manufacturing) 21,500 20,900 21,900 19,500 20,700 18,200 Over time viscosity (after 1 month) 21,300 21,300 20,100 19,300 20,500 15,300 Over time viscosity (after 3 months) 20,800 20,300 18,100 18,500 19,400 11,700 Lapse rate 1.03 1.03 1.21 1.05 1.07 1.56

As shown in Table 1, in the case of the vinyl chloride-based polymer composition prepared according to the present invention, it was confirmed that the viscosity stability is superior to Comparative Example 1, which does not contain higher fatty acids.

Claims (16)

Vinyl chloride polymers; And at least one higher fatty acid selected from the group consisting of castor oil fatty acid, dehydrated castor oil fatty acid, hardened castor oil fatty acid, sebacic acid and undecylenic acid;
The vinyl chloride-based polymer has an average particle diameter of 0.24 μm to 2.0 μm,
The higher fatty acid is a vinyl chloride-based polymer composition that is contained in an amount of more than 0 parts by weight to 5 parts by weight or less based on 100 parts by weight of the vinyl chloride-based polymer. According to claim 1,
The vinyl chloride-based polymer is a vinyl chloride-based polymer composition comprising 50 to 100% by weight of repeat units derived from vinyl chloride monomer and 0 to 50% by weight of repeat units derived from vinyl monomer. According to claim 1,
The vinyl chloride-based polymer has an average particle diameter of 0.5 μm to 1.5 μm. According to claim 1,
The higher fatty acid is a vinyl chloride-based polymer composition that is included in a mixed state on the three-dimensional network (network) of the vinyl chloride-based polymer. delete delete According to claim 1,
The higher fatty acid is a vinyl chloride-based polymer composition that is a higher fatty acid saponified. Preparing a vinyl chloride-based polymer latex comprising a vinyl chloride-based polymer having an average particle diameter of 0.24 ㎛ to 2.0 ㎛ (S1);
Adding and stirring one or more higher fatty acids selected from the group consisting of castor oil fatty acid, dehydrated castor oil fatty acid, hardened castor oil fatty acid, sebacic acid and undecylenic acid in the prepared vinyl chloride polymer latex (S2) ); And
Drying the stirred vinyl chloride-based polymer latex to obtain a vinyl chloride-based polymer powder (S3),
The higher fatty acid is a method of preparing a vinyl chloride-based polymer composition that is added in an amount of more than 0 parts by weight to 5 parts by weight or less based on 100 parts by weight of the vinyl chloride-based polymer. The method of claim 8,
The production of the vinyl chloride-based polymer latex in the step (S1) is carried out by an emulsion polymerization method, a fine suspension polymerization method or a suspension polymerization method. The method of claim 8,
A method for preparing a vinyl chloride-based polymer composition comprising the step of saponification of a higher fatty acid with a saponifier prior to the introduction of the higher fatty acid in step (S2). The method of claim 10,
The saponification agent is a method for producing a vinyl chloride-based polymer composition that is used in a molar ratio of 0.1 to 5 mol with respect to 1 mol of the higher fatty acid. The vinyl chloride-based polymer composition according to claim 1, further comprising a plasticizer. The method of claim 12,
The plasticizer is a vinyl chloride-based polymer composition of at least one selected from the group consisting of phosphoric acid ester plasticizer, aliphatic dibasic ester plasticizer, epoxy plasticizer and polyester plasticizer. The method of claim 12,
The plasticizer is a vinyl chloride-based polymer composition that is contained in 1 to 200 parts by weight based on 100 parts by weight of the vinyl chloride-based polymer. The method of claim 12,
The vinyl chloride-based polymer composition is a vinyl chloride-based polymer composition having an initial viscosity of more than 18,200 cP to 25,000 cp or less. The method of claim 15,
The vinyl chloride-based polymer composition is a vinyl chloride-based polymer composition having an initial viscosity and a change in viscosity over time after 3 months of less than 1.56.