JPS5834487B2 - Method for producing granular copolymer - Google Patents

Description

Detailed Description of the Invention N-(alkoxymethyl)acrylamide in the present invention refers to N-(π-butoxymethyl)acrylamide,
It means N-(alkoxymethyl)acrylamides such as N-(isobutoxymethyl)acrylamide, N-(hexoxymethyl)acrylamide, N-(octyloxymethyl)acrylamide, and N-(lauryloxymethyl)acrylamide.

The present invention relates to a method for producing a copolymer obtained by copolymerizing N-(alkoxymethyl)acrylamide and an acrylic monomer or a vinyl monomer in granular form.
The purpose of this is that a copolymer formed by copolymerizing N-(alkoxymethyl)acrylamide and an acrylic monomer or a vinyl monomer in granular form is soluble in an organic solvent; A copolymer dissolved in an organic solvent has good storage stability, and can be condensed and crosslinked by heating it at 200°C or less for 60 seconds without adding a condensation catalyst or crosslinking agent. By rapidly advancing the reaction, a condensed resin with solvent resistance and heat melting resistance can be obtained, and by adjusting the condensation density,
Flexibility and hardness can be selectively imparted to condensed resins,
Granules that can be used as coating agents, such as everpleat processing of textile products that require flexibility and washing resistance, raw materials for waterproofing, binding agents for non-woven fabrics, and raw materials for paints that require hardness. The purpose is to provide a copolymer.

Conventional coating synthetic resins made by copolymerizing N-(alkoxymethyl)acrylamide with vinyl monomers or acrylic monomers include, as an example of solution polymerization, Patent Publication No. 15610 of 1962; 1971 No. 12908
No. 10090 of 1970, etc., but these use a solvent with a chain transfer constant to cause the copolymerization reaction, and the copolymer is of course soluble in organic solvents, but it is granular. Since it was not a copolymerization method, there was a risk that unreacted substances remained and toxicity remained.

Also, as an example of emulsion polymerization, Patent Publication No. 556 of 1962
No. 5, No. 6429 of 1970, No. 85 of 1971
No. 53, No. 4327 of 1972, etc., but these often use lidox catalysts that can perform low-temperature polymerization at a copolymerization temperature of 60°C or less, and the products are also soluble in organic solvents. However, it is only after adding post-additives such as a condensation catalyst and crosslinking agent that the condensation and crosslinking reaction proceeds through heat treatment, resulting in a condensation resin that has solvent resistance and heat melt resistance. In addition to requiring the addition of post-additives, the composition after the addition of post-additives undergoes a condensation cross-linking reaction and has no storage stability, and the condensed resin after heat treatment becomes hard, making it difficult to coat the fibers after coating. Alternatively, there was a drawback that the texture of the painted surface was deteriorated.

We also attempted to copolymerize other copolymerizable modified monomers such as tetrahydrofuran monomethacrylate, glycicyl methacrylate, and glycerin monomethacrylate, but they are soluble in organic solvents and cannot be condensed by heat treatment at 200°C or less for seconds. The crosslinking reaction progresses rapidly, giving the condensed resin heat-resistant, melt-resistant,
It has not been possible to obtain a granular copolymer that exhibits solvent resistance.

The present invention was achieved by selecting copolymerization conditions as a result of various copolymerization experiments of N-(alkoxymethyl)acrylamide and acrylic monomers or vinyl monomers. We have discovered a method for producing particulate copolymers with properties.

The present invention is based on this. The present invention uses N-(alkoxymethyl)acrylamide and an acrylic monomer or vinyl monomer as a suspending agent, a buffering inorganic salt such as dibasic sodium phosphate, a polymerization regulator, and azobisbutinitrile. A copolymer soluble in an organic solvent, which is formed by granular copolymerization in the presence of a polymerization catalyst such as
By heating for less than 0 seconds, the copolymer undergoes a rapid condensation and crosslinking reaction to become a solvent-resistant and heat-melting resistant condensed resin, and the condensation density can be adjusted by adjusting the heat treatment temperature and time. This is a method for producing a particulate copolymer having the property of selectively imparting flexibility and hardness to a condensed resin.

Next, an example will be explained.

Example 1 As a suspending agent, 0.4 g of sodium polyacrylate, molecular weight 10. OOO~1oo, ooo polyoxyethylene glycol 0.1g, dibasic sodium phosphate 3g as a buffering agent
and 2 g of sodium chloride are dissolved in 450 g of water to make a suspension.The suspension is placed in a reaction flask equipped with a stirrer and a condenser, heated and stirred, and the temperature of the suspension is 6
After the temperature reaches 5°C, first monomer N-(alkoxymethyl) acrylamide 4g tylacrylate 144g second monomer tylacrylate 35g crylonitrile 25g polymerization catalyst azobisisobutyronitrile 0.759 polymerization agent tertiary A mixture of 0.069 butyl mercaptan was added to the suspension in the reaction flask, the temperature of the composition was adjusted to 700-71°C, and the rotation speed of the stirrer was increased to 360P.
, P, M, for 2 hours, and then at 72° to 73°C for 3 hours.
A time-thermal reaction is allowed to occur.

A colorless and transparent granular copolymer with a diameter of 0.5 to 17 ft TIL was then obtained.

This copolymer is soluble in organic solvents such as toluene and ethyl acetate.

Although this granular copolymer was dissolved in a toluene solution with a solid content of 16% by weight, the rotor failed in a B-type viscometer.

4. When measured with torque 6R, P, M, 4 at 200c
．． 000C, P, S, (7) Value and ivy.

The solution of this granular copolymer used in the above viscosity measurement, that is, the solution without any subsequent addition of condensation catalyst or crosslinking agent, was applied to nylon taffeta, dried at room temperature, and then blown with hot air at 160°C. A heat treatment was carried out for a spraying time of 50 seconds to cause a condensation crosslinking reaction in the copolymer of the coating layer to form a coating layer of condensed resin.

Even if this coating layer is immersed in percrene for 30 minutes, the amount of dissolved matter in the coating layer is apparently "zero", and its JIS-630
1-1962 (7) Standard Gnoll swelling rate was "small".

This heat-treated coating layer does not dissolve in perchloromethane, indicating that the solvent resistance of the condensed resin coating layer is nearly perfect.

This also shows that since the copolymer was subjected to a condensation reaction by heat treatment, the condensed resin had no heat meltability.

When the copolymer coating layer was heat-treated at 160'C for 30 seconds and immersed in percrene for 30 minutes, the dissolved content was apparently "zero" and the degree of swelling was 45%.

Even with this heat treatment, the condensation and crosslinking reaction of the coating layer progresses to a certain extent and is completed, and the solvent resistance is considered to be sufficient.The degree of swelling indicates that the coating layer has flexibility after the condensation reaction. It shows.

The copolymer coating layer heat-treated at 200°C for 20 seconds was insoluble in the same dissolution test as above, and 3 in the swelling test above.
It was 0%.

The fact that the granular copolymer obtained by the above production method has the above-mentioned properties is due to the fact that the condensation crosslinking density can be increased by selecting the temperature and time of the heat treatment method in which the granular copolymer is subjected to a condensation crosslinking reaction. By adjusting the height of the granular copolymer, increasing the temperature and increasing the time, and achieving a high condensation density with no degree of swelling, the condensation resin becomes robust and a solid coating layer can be formed, making the granular copolymer transparent. This shows that it can be used as a robust paint raw material in combination with its properties, but it can also be used as a material with a low condensation density and swelling degree by using a relatively low heat treatment temperature and shortening the heat treatment time. The condensed resin then becomes flexible and can form a flexible coating layer, which combines with the transparency of the granular copolymer to enable everpleat processing of fibers that require flexibility and wash resistance. This shows that it can be used as a binder used in the production of nonwoven fabrics.

Example 2 The composition of the suspension containing the buffer, the amounts of the first and second monomers, and the amount of polymerization catalyst were the same as in Example 1, and the reaction method was also the same. went.

However, only the amount of polymerization regulator was set to 0.04 g.

The yield of the colorless and transparent granular copolymer thus obtained was the first
It increased by about 1% from the example.

The viscosity of this copolymer was determined to be 6.000C, P, S by the same viscosity measuring method as in the first example.

When this granular copolymer is dissolved in an organic solvent as in the first example and used as a coating material without the subsequent addition of a condensation catalyst or a crosslinking agent, and subjected to the same heat treatment as in the first example,
The coating layer had substantially the same properties as in the first example.

That is, in the heat treatment at 160°C for 50 seconds, the solubility was "zero" in the dissolution test with perchloren similar to the first example, "small" in the swelling degree test similar to the first example, and
The product heat-treated for 30 seconds was insoluble in percrene dissolution test and 35% in swelling test.

The one heated at 200'C for 20 seconds was insoluble in the perclene dissolution test and 30% in the swelling test.

Example 3 The composition of the suspension containing the buffer was the same as in the first example, except that 2 g of the first monomer, 136 g of butyl acrylate as the second monomer, 35 g of ethyl acrylate, and acrylonitrile were added. was 25g, 2g of 2-hydroxyethyl methacrylate was newly added to the second monomer, and the amount of polymerization regulator was 0.035g, and the granular copolymerization reaction was carried out as follows:
This was carried out in the same manner as in the first example.

The colorless and transparent granular copolymer obtained by this reaction is
As in Example 1, it is soluble in organic solvents, and the viscosity test shows that it is 50. It was OOC, P, S.

This granular copolymer was dissolved in a toluene solvent and coated in the same manner as in the first example without adding a condensation catalyst, a crosslinking agent, etc., and heat treated.

In this case, when the heat treatment was carried out at 160° C. for 50 seconds, perclene was insoluble in the dissolution test, and the degree of swelling was "small" in the swelling test.

The sample heated at 160'C for 30 seconds partially dissolved in the percrene dissolution test.

This indicates that this level of heat treatment does not provide sufficient solvent resistance.

The product heat-treated at 200'C for 20 seconds was insoluble in the perclene dissolution test and 13% in the swelling test.

Example 4 The composition of the suspension containing the buffer was the same as in the first example, but the first monomer was 1.5 g, the second monomer was 137 g of butyl acrylate, 40 g of ethyl acrylate, and acrylonitrile. The granular copolymerization reaction was carried out in the same manner as in the first example using 20 g of 2-hydroxyethyl methacrylate and 0.02 g of the polymerization regulator to obtain a colorless and transparent granular copolymer. Ta.

This particulate copolymer was soluble in organic solvents as in the first example, and the viscosity measured by the same viscosity measurement method as in the previous example was 8.0 OOC, P, S.

The coating layer was formed by dissolving this granular copolymer in an organic solvent in the same manner as in the first example, and heat-treating it in the same manner as in the first example without adding a condensation catalyst crosslinking agent or the like. , 160°C in the same dissolution test and swelling degree as in the first example.
The one that was heat treated for 50 seconds had a solubility of ``zero'' and the swelling degree of ``small'', and the one that was heat treated at 60°C for 30 seconds dissolved in the dissolution test (this level of heat treatment had insufficient solvent resistance), and the swelling was 2oo.
When heated for 20 seconds at °C, the solubility was "zero" and the degree of swelling was 25%.

As a result of conducting various experiments in addition to the above examples, the following was found.

(1) The second monomer copolymerized with the first monomer N-(alkoxymethyl)acrylamide cannot copolymerize with acidic monomers such as acrylic acid and methacrylic acid; One or more of acrylates or methacrylates such as ethyl, propyl, butyl, and lauryl, acrylic monomers such as acrylonitrile, and vinyl monomers such as styrene and vinyl acetate are used in the copolymerization.

Additionally, a small amount of monoacrylate or monomethacrylate of an alkyl group having a hydroxyl group such as 2-hydroxyethyl, 2-hydroxypropyl, 3-chloro-2-hydroxypropyl, etc. may be used in combination.

In addition, when the amount of the first monomer is small, the condensation crosslinking density of the produced granular copolymer composition due to a certain heat treatment becomes small,
Swellability occurs, and if the amount of the first monomer is 100%, the condensation crosslink density due to a certain heat treatment will be 100%.

(2) As the suspending agent, one or more of polysodium acrylate, polysodium methacrylate, popal, casein, polyethylene glycols, etc. is used in an amount of about 0.2% by weight based on the water used for granular polymerization.

(Additionally, a surfactant such as sodium lauryl sulfonate or sodium dodecylbenzenesulfonate may be used in an amount of 0.01% by weight based on the water used for granular polymerization.

)(3) As the buffer, it is preferable to use buffering inorganic salts such as dibasic sodium phosphate.

(4) As a polymerization regulator, a compound having a large chain transfer constant for acrylic monomers and vinyl monomers,
That is, it is preferable to use one or more polymerization regulators such as mercaptans, carbon tetrachloride, and isopropanol in combination.

(5) Polymerization catalysts include azo polymerization catalysts such as azobisbutyronitrile, and peroxides that are oil-soluble and decomposable below about 65°C, other than peroxides that decompose into acidic compounds. good.

As mentioned above, the granular copolymer of the present invention is soluble in an organic solvent, and by heating it at 200°C or less for 60 seconds without adding a condensation catalyst or a crosslinking agent, etc. The condensation and crosslinking reaction of the copolymer can be rapidly progressed to produce a solvent-resistant and heat-melting-resistant condensation resin, and the condensation density can be adjusted high or low by adjusting the temperature and time of the heat treatment. Hardness and flexibility can be selectively imparted to the material.

Therefore, the granular copolymer produced by the method of the present invention can be used as a raw material for paints that require hardness and fastness, as an everpleating agent for textile products that require flexibility and washing resistance, and as a waterproofing agent. It is suitable as a coating agent such as a binder for manufacturing non-woven fabrics, and has uses such as floor desks.

Also, since it is produced by a granular copolymerization reaction,
The purity of the product is high, and there is no risk of unreacted substances remaining in the solvent and toxicity remaining in the product as in the case of solution copolymerization.

Claims (1)

[Claims] 1 At least 0.5 to 2% by weight of N-(alkoxymethyl)acrylamide and 98 to 99.5% of an acrylic monomer or vinyl monomer as a suspending agent,
In the presence of a buffering inorganic salt such as dibasic sodium phosphate, a polymerization regulator, and a polymerization catalyst such as azobisbutyronitrile, at a temperature of 200°C or less without the subsequent addition of a condensation catalyst or crosslinking agent, etc. A method for producing a granular copolymer, characterized in that the granular copolymerization is carried out by subjecting it to a heat treatment for up to 60 seconds.