JPH06298921A - Macromonomer and its polymer - Google Patents

Abstract

PURPOSE:To provide a macromonomer having excellent microbial degradability and alkali hydrolizability and useful as a polymer alloy-forming agent and solubilization assistant for polymeric materials by compounding a lactic acid- based resin and a low-molecular weight monomer having a specific structure. CONSTITUTION:The macromonomer is composed of (A) a resin having a weight- average molecular weight of 1,000-50,000 and selected from (i) a polylactic acid derived from lactic acid and/or a cyclic lactide, (ii) a lactic acid random copolymer resin derived from lactic acid and/or a cyclic lactide and a mercaptocarboxylic acid and (iii) a lactic acid block copolymer resin derived from polylactic acid and a polymercaptocarboxylic acid, etc., and having a lactic acid content of 30-95wt.% and (B) a low-molecular weight monomer having a molecular weight of <=500 and containing one functional group selected from isocyanate, glycidyl, etc., and an ethylenic double bond on the same molecular terminal. The macromonomer is expressed by formula (X is bonding group produced by reacting the component A with the component B; Y is univalent residue obtained by removing terminal group from the component A; R1 is H or CH3; R2 is H, carboxyl, etc.).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel macromonomer having good reactivity, microbial degradability and alkali hydrolyzability.

More specifically, the present invention relates to the above macromonomers useful as modifiers for various plastics, polymers derived from the macromonomers, methods of use and the like.

[0003]

2. Description of the Related Art In recent years, various kinds of macromonomers have been proposed as raw materials for producing highly controlled graft polymers.

In particular, as a method proposed by Milkovich et al. In 1974, a living polystyrene end obtained by a living anionic polymerization method is treated with ethylene oxide, and a polystyrene macromonomer obtained by reacting a precursor thereof with methacryl chloride is used. Known as the early macromonomer.

Then, polystyrene macromonomers obtained by the living anion method marketed by ARCO Chemical Co., Ltd., polymethyl methacrylate acrylic macromonomers obtained by the radical method marketed by Toagosei Kagaku Co., and polybutyl butyl macromonomers. , And horiacrylonitrile macromonomer are well known.

[0006] In addition, in addition, a method for stopping cation living such as polyethylene oxide macromonomer, polytetrahydrofuran macromonomer, polyisoprene macromonomer, poly-2-vinylpyridine macromonomer, polydimethylpolysiloxane macromonomer and anion living stop or start. Macromonomers obtained by the applied method have been reported.

Particularly, most recently, JP-A-5-70546 is used.
In JP-A-5-59185, there is a report on a silicon-containing macromonomer, and in JP-A-4-304.
In 204, there is a report on a macromonomer having a vinyl alcohol unit and an ethylene unit.

Further, Japanese Patent Laid-Open No. 5-70754 discloses an example of an acrylic copolymer resin composition using a polystyrene macromonomer.

However, no macromonomer having both microbial degradability and alkali hydrolyzability has been known so far, and a microbial decomposition product or an alkali hydrolysis product of the macromonomer is harmless to the global environment, especially to humans and animals and plants. There is nothing that shows such a property.

Further, when plastics products up to now are finally landfilled as garbage, they are rarely completely decomposed, which causes social problems as environmental pollutants. There is. There is a strong demand for improvement in high functionality of polymer materials represented by imparting disintegration properties to plastics, and in that sense, a new macromonomer is desired.

[0011]

In view of the above, the present invention mainly provides a macromonomer having the following three properties, and alloying and modifying a polymer material using the macromonomer. The invention provides a polymer that facilitates the process, and a method of using the polymer.

First, it has excellent microbial degradability and alkali hydrolyzability.

Second, most of the decay and decomposition products have almost no harm to the global environment, especially humans and animals and plants.

Thirdly, it is rich in polymerization reactivity, and the polymer can be preferably used as a polymer alloying agent or a compatibilizing aid for polymer materials.

[0015]

As a result of intensive studies to solve the above problems, the present inventors have found that a macromonomer represented by the following formula 1 is preferable, and also from the macromonomer of the formula 1 The derived polymer is useful as a polymer alloying compatibilizer for general-purpose plastics,
The present invention has been achieved by finding out that a polymer having a porous structure can be provided.

That is, the present invention provides [I] a polylactic acid derived from lactic acid and / or a cyclic lactide, which has a weight average molecular weight of 1,000 to 50,000. A lactic acid random copolymer resin derived from (B) lactic acid and / or a cyclic lactide and one selected from mercaptocarboxylic acid, hydroxycarboxylic acids other than lactic acid, aminocarboxylic acid and the like, and (C) polylactic acid, and poly (lactic acid) Lactic acid block copolymer having a lactic acid content of 30 to 95% by weight, which is derived from mercaptocarboxylic acid, polyhydroxycarboxylic acid derived from hydroxycarboxylic acid other than lactic acid, and one selected from polyaminocarboxylic acid Any of the resins [II] having a molecular weight of 500 or less, an isocyanate group,
Derived from a low-molecular monomer having an ethylenic double bond and one functional group selected from the group consisting of a glycidyl group, an acid anhydride group, an amide group, a carboxyl group and a hydroxyl group at the same molecular end. And a macromonomer represented by the following formula 1.

[0017]

[Chemical 2] (In the formula, X is a hydroxyl group which is a terminal functional group of [I],
One kind of functional group selected from a carboxyl group, an amino group, a mercapto group, etc. and one kind selected from the group consisting of an isocyanate group [II], a glycidyl group, an acid anhydride group, a carboxyl group and a hydroxyl group. Y is a linking group formed by chemically reacting with a functional group, and Y is a monovalent polylactic acid group or a lactic acid random copolymer that is left after the terminal functional group of [I] involved in the reaction with [II] is removed. Means a polymer resin group or a lactic acid block copolymer resin group, R ¹ is hydrogen or a methyl group, R ² is hydrogen, a carboxyl group or a carbon number of 1 to 20.
Means an alkyl ester group. ) Preferably, the weight average molecular weight is in the range of 1,000 to 20,000, and [II] has an isocyanate group and an ethylenic double bond as the [I] having a hydroxyl group or an amino group as a terminal functional group. A low molecular weight monomer having a carboxyl group and a low molecular weight monomer having an ethylenic double bond, and a reaction molar equivalent of a hydroxyl group or an amino group of [I] and an isocyanate group or a carboxyl group of [II]. The macromonomer of the formula 1 which is obtained by reacting at a ratio of about 1: 1 is preferable.

More preferably, the weight average molecular weight is in the range of 1,000 to 20,000 and [II] is a hydroxyl group and an ethylenic double bond as opposed to [I] having a terminal functional group having a carboxyl group. And a low molecular weight monomer having a glycidoxy group and a low molecular weight monomer having an ethylenic double bond at a reaction molar equivalent ratio of the carboxyl group of [I] and the hydroxyl group or glycidoxy group of [II]. More preferred are macromonomers of formula 1 characterized by being obtained by reacting at approximately 1: 1.

Furthermore, in [I], the carboxyl group at one end is alkyl-esterified with a higher alcohol, or the hydroxyl group at one end is halide-treated with an alkyl halide.
1 selected from the group consisting of 5,000 polylactic acid, polyhydroxycarboxylic acid excluding polylactic acid, polyaminocarboxylic acid, polyester having a carboxyl group or hydroxyl group at one terminal, and polyether polyester having a carboxyl group or hydroxyl group at one terminal. Most preferred are macromonomers of formula 1 which are characterized in that they are lactic acid block copolymers (C) derived from one or more resins.

Further, the macromonomer represented by the formula 1 and having a weight average molecular weight of 1,200 to 10,000 is particularly most preferable.

In the present invention, the macromonomer represented by the formula 1 is used in the range of 0.1 to 90% by weight, and one or more kinds of other unsaturated monomers copolymerizable with the macromonomer are used. A polymer produced by copolymerization with 9 to 10% by weight. It is a polymer obtained by grafting the macromonomer of the formula 1 to another polymer in the range of 1 to 50% by weight.

After the polymer is formed into a thread or a film, it is further subjected to an alkali hydrolysis treatment to form a fine porous structure, and the processed product is used for the production of a breathable film and a breathable nonwoven fabric. preferable.

It is much more preferred to utilize the polymer as a polymeric alloying agent or compatibilizing aid.

The present invention will be described in more detail below.

[I] of the present invention is one resin selected from (A), (B), and (C) summarized below, and has at least a hydroxyl group, a carboxyl group as a terminal functional group, It contains one kind of functional group selected from an amino group and a mercapto group, and has a weight average molecular weight of 1,000 to
It is a resin in the range of 50,000. (A) Polylactic acid. (B) Lactic acid random copolymer resin. (C) A lactic acid block copolymer resin having a lactic acid content of 30 to 95% by weight.

The (A) polylactic acid is, for example, D type,
Prepared by a known esterification and / or ring-opening polycondensation reaction using a cyclic lactide which is L-type, D, or L-complex lactic acid and / or a lactic acid derivative as a raw material.
Weight average molecular weight in the range of 1,000 to 50,000,
A typical example is polylactic acid having either a hydroxyl group or a carboxyl group as a functional group at one end.

Polylactic acid having a number average degree of polymerization represented by a value converted from at least a weight average molecular weight of 10 to 5,000, particularly preferably a number average degree of polymerization of 20 to 3,000 is a highly preferable example.

If necessary, (A) is an alkyl lactate (alkyl having 1 to 30 carbon atoms which may be branched) ester, an alkyl monoalcohol having 1 to 30 carbon atoms which may be branched, 1 to 3 carbon atoms that may be branched
In the presence of a known polycondensation catalyst, an alkyl monocarboxylic acid of 0 is used as an auxiliary material in a very small amount.
Polylactic acid obtained by esterification or ring-opening polycondensation with the lactic acid or cyclic lactide and alkylated at one end is also preferably included.

The above-mentioned (B) lactic acid random copolymer resin is
The first component of lactic acid or cyclic lactide, and further mercaptocarboxylic acids such as mercaptoacetic acid and mercaptopropionic acid, hydroxycarboxylic acids such as hydroxyacetic acid and hydroxypropionic acid, and amino acids such as 11-aminoundecanoic acid and 12-aminododecanoic acid. It is induced by esterification or ring-opening polycondensation in one step or two or more steps in the presence of a known polycondensation catalyst using one or more second components selected from carboxylic acids and the like. A typical example is a resin in which lactic acid and the second component are basically bonded at random to form a polymer.

Further, the above (B) has a weight average molecular weight of 1,
It is preferable to have at least one selected from a hydroxyl group, a carboxyl group, a mercapto group, and an amino group as the functional group on one end, in the range of 000 to 50,000.
Particularly preferably, the weight average molecular weight is 1,000 to 30,0.
00, most preferably in the range of 2,000 to 10,000.

The (C) lactic acid block copolymer resin has a polylactic acid chain length content of 30 to 95 in the resin.
It is a resin that occupies weight% and is introduced in a block shape. Although not particularly limited, a resin obtained by the following method is typical.

For example, the weight average molecular weight is 500 to 10,
30 to 95% by weight of polylactic acid in the range of 000 and polyhydroxycarboxylic acid excluding lactic acid, polyaminocarboxylic acid, polyester having one terminal carboxyl group or hydroxyl group, polyether polyester having one terminal carboxyl group or hydroxyl group 1 or 2
This is a method in which 5 to 70% by weight of a seed resin (hereinafter simply referred to as a second component resin for block copolymerization) is subjected to a coupling reaction to induce it.

In the above method, one of the polyester resin having a carboxyl group or hydroxyl group at one terminal and the polyether polyester resin having a carboxyl group or hydroxyl group at one terminal is used as the second component resin for block copolymerization. This is a preferred example.

In the production method (C), polylactic acid having a weight average molecular weight in the range of 500 to 10,000 is previously selected from monoglycidyl ester compounds, monoglycidyl ether compounds and monoisocyanate compounds. After acting as a stabilizer, a precursor in which the carboxyl group or the hydroxyl group at one terminal of polylactic acid is selectively sealed and stabilized, and then reacted with the second component resin for block copolymerization The method of obtaining is also preferable.

As another method for producing (C), a polylactic acid having a weight average molecular weight in the range of 500 to 10,000 is previously stabilized with an alkyl acid halide represented by alkyl acid chloride or alkyl acid bromide. The method obtained by acting the agent on the hydroxyl group at one terminal of polylactic acid to form a precursor in which the hydroxyl terminal is blocked / stabilized and then reacting with the second component resin of the blocking agent resin is This is a preferred example.

The above-mentioned polylactic acid precursors include those treated with a separate protective agent other than those mentioned above, and selectively deactivate one end functional group of polylactic acid with a known stabilizer. There is no problem by adopting the above method as appropriate.

Precursors derived from alkyl lactate and lactic acid or cyclic lactide are also good examples.

Other known stabilizers are higher monoalcohols having 12 to 30 carbon atoms which may be branched, such as stearyl alcohol and isostearyl alcohol, and stearic acid and isostearic acid. There are higher monocarboxylic acids having 12 to 30 carbon atoms which may be branched.

Further, in the production of (C) using the precursor, a basic substance can be appropriately employed as a scavenger for scavenging hydrogen halide generated during the reaction step. In selecting a basic substance, it is preferable to select a basic substance that does not cause polylactic acid to hydrolyze, and examples thereof include substances such as pyridine, triethylamine and sodium hydrogen carbonate. When the alkyl acid halides are allowed to act, the reaction is preferably carried out at 60 ° C. or lower, particularly preferably 0 ° C. or lower, in order to suppress side reactions. The alkyl acid halides are represented by propionic acid chloride, propionic acid bromide and the like.

There is no particular limitation on the third component substance used as necessary when coupling the polylactic acid with the second component resin of the blocking agent resin, but known diamine compounds, diisocyanate compounds, A diglycidyl compound etc. are mentioned as a preferable example.

In the following description, [I] is collectively referred to as a lactic acid resin.

[II] described in the present invention means that one kind of functional group selected from an isocyanate group, a glycidyl group, an acid anhydride group, a carboxyl group and a hydroxyl group and an ethylenic double bond in the same molecule. Has a molecular weight of 500
It is less than a low molecular weight monomer. In the following explanation, [I
I] is collectively referred to as a low molecular weight monomer.

The low molecular weight monomer contains, if necessary, one kind of functional group selected from a halide group, an amide group, a phosphoric acid group, a sulfonic acid group and a silanol group and an ethylenic double bond. In addition to molecular monomers, unsaturated imides such as maleimide, phenylmaleimide and benzylmaleimide, allyl compounds such as allyl acetate and allyl chloride, methacrylamidopropyldimethylamine and its salts and quaternary salts are also included.

Examples of the low molecular weight monomer containing an isocyanate group and an ethylenic double bond include acryloyl isocyanates, methacryloyl isocyanates and isopropenylphenyl isocyanates. Specific examples of the acryloyl isocyanates include acryloyl isocyanate, acryloyloxyethyl isocyanate, and acryloyloxypropyl isocyanate, and specific examples of the methacryloyl isocyanates include methacryloyl isocyanate, methacryloyloxyethyl isocyanate, and methacryloyloxypropyl isocyanate. In the case of isopropenyl phenyl isocyanate, specifically, m-isopropenyl-α, α'-dimethylbenzyl isocyanate,
A typical example is p-isopropenyl-α, α'-dimethylbenzyl isocyanate. A typical example is a 1: 1 adduct of the following (meth) acrylic acid hydroxyalkyl ester and 2,4-tolylene diisocyanate or isophorone diisocyanate.

Typical examples of the low molecular weight monomer containing a glycidyl group and an ethylenic double bond include glycidyl methacrylate and glycidyl acrylate.

Typical examples of the low molecular weight monomer containing an acid anhydride group and an ethylenic double bond are maleic anhydride and itaconic anhydride.

Examples of the low molecular weight monomer containing a carboxyl group and an ethylenic double bond include (meth) acrylic acids represented by methacrylic acid and acrylic acid, maleic acid monopropyl ester and maleic acid monobutyl ester. Representative examples include maleic acid monoalkyl esters, fumaric acid monopropyl ester, fumaric acid monoalkyl esters represented by fumaric acid monobutyl ester, maleic acid, fumaric acid, and itaconic acid.

As the low molecular weight monomer containing a hydroxyl group and an ethylenic double bond, (meth) acrylic acid hydroxyesters represented by hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate and hydroxypropyl acrylate. Other examples are isopropenylphenol and vinylphenol.

The low molecular weight monomer containing a halide group and an ethylenic double bond is represented by allyl chloride and allyl bromide.

Examples of the low molecular weight monomer containing an amide group and an ethylenic double bond include acrylamide, methacrylamide, N-methyl acrylamide, N-ethyl acrylamide, N, N-dimethyl acrylamide and diacetone acrylamide. Typical examples include acrylamides and salts thereof or quaternary salts, N-methylol acrylamides and the like.

Examples of the low molecular weight monomer containing a phosphoric acid group and an ethylenic double bond include monosubstituted phosphoric acid esterified products of the above-mentioned hydroxy (meth) acrylates.

Examples of the low molecular weight monomer having a sulfonic acid group and an ethylenic double bond include methacrylamidopropane sulfonic acid and salts thereof.

Examples of the low molecular weight monomer containing a silanol group and an ethylenic double bond include vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane, vinyldiethoxymethylsilane and acryloylpropoxytrimethoxysilane. Representative examples include vinylsilanes such as acryloylpropyltriethoxysilane, acryloylpropoxydimethoxymethylsilane, acroylpropyldiethoxymethylsilane, and vinylhydrogensilane.

The macromonomer of the present invention can be said to be a lactic acid resin monomer derived from a lactic acid resin and a low molecular weight monomer.

The macromonomer of the present invention basically has, as represented by the above formula 1, a polymerizable reactive group described below and a monovalent lactic acid-based resin group (Y) bonded to one end. It is a macromonomer linked by a group (X).

The polymerizable functional group is preferably one group selected from methacryloyl group, acryloyl group, acrylamide group, methacrylamide group, isopropenyl group, allyl group, maleyl group, fumar group and the like. .

The macromonomer of the present invention has a weight average molecular weight of 1,200 to 50,500, preferably 1,
200 to 35,000, particularly preferably 1,20
0 to 10,000 is good. The reason is that the effect of imparting the polymer alloy compatibility as various macromonomer components for resin modification is low at 1,200 or less.
This is because the above-mentioned materials have high melt viscosity characteristics and tend to lack compatibility with various synthetic resins.

In formula (1), (X) has already been described above, but 1 selected from the terminal functional groups of the lactic acid resin, such as hydroxyl group, carboxyl group, amino group and mercapto group.
A functional group of one species and a functional group of one selected from an isocyanate group, a glycidyl group, an acid anhydride group, a carboxyl group, and a hydroxyl group of a low-molecular monomer are reacted in a stoichiometric amount to generate. It is a linking group. However, in the present invention, (X) is further selected from the above-mentioned terminal functional group of the lactic acid-based resin, and a halide group, an amide group, a phosphoric acid group, a sulfonic acid group, a silanol group of a low molecular weight monomer, if necessary. It is also included in a bonding group formed by reacting the above-mentioned one functional group stoichiometrically. Particularly preferred bond-forming group (preferred X)
Is represented by Equation 2.

[0059]

[Chemical 3] (However, R ³ has 1 to 2 carbon atoms which may have a branch.
An alkylene group represented by an integer of 0, R ⁴ represents hydrogen or an alkyl group represented by an integer of 1 to 20 carbon atoms which may have a branch. ) More specifically, when the lactic acid-based resin is a macromonomer of the present invention derived from polylactic acid (as defined in A above), Y in Formula 1 is
It is a monovalent polymer containing a lactic acid repeating unit of any of D type, L type, and D / L complex type, and is defined as a monovalent polylactic acid group in the present invention.

When the lactic acid-based resin is a macromonomer of the present invention derived from a lactic acid random copolymer resin (defined in B above), Y in the formula 1 is D type, L type, D / L composite type. 1 type selected from any one of lactic acid, hydroxycarboxylic acid, aminocarboxylic acid, mercaptocarboxylic acid, polyester whose terminal functional group is a carboxyl group or hydroxyl group, and polyether polyester whose terminal functional group is a carboxyl group or hydroxyl group Alternatively, a monovalent random polymer containing, as a repeating unit, any one of lactic acid obtained by polycondensation in a one-step or two-step reaction using two kinds of second copolymerization components as raw materials and a second copolymerization component as a repeating unit. In the present invention, it is defined as a monovalent lactic acid random copolymer resin group.

The above-mentioned hydroxycarboxylic acid is represented by ε-caprolactam, hydroxyacetic acid, hydroxypropionic acid and the like.

The aminocarboxylic acid is typically D / L alanine, 11-aminoundecanoic acid, 12-aminododecanoic acid, polyamide resin having a carboxyl group or amino group at one end.

The above-mentioned mercaptocarboxylic acid is represented by mercaptoacetic acid and mercaptopropionic acid.

The above-mentioned polyamide resin having a carboxyl group or an amino group as the terminal functional group includes, for example, dibasic acids such as adipic acid, sebacic acid, azelaic acid and dimer acid, and hexamethylenediamine and metaxylylenediamine. Resins derived from diamines as raw materials, and other compounds such as caprolactam ring-opening addition polymer, poly-
11-aminoundecanoic acid, poly-12-aminododecanoic acid and the like are mentioned, and those having a weight average molecular weight of less than 10,000, preferably less than 2500 are mentioned as preferable examples.

Furthermore, the polyester whose terminal functional group is a carboxyl group or a hydroxyl group means aromatic dibasic acids such as isophthalic acid, terephthalic acid and phthalic anhydride, and / or adipic acid, succinic acid, succinic anhydride, Aliphatic dibasic acids such as sebacic acid and azelaic acid (in the following description, aromatic dibasic acids and aliphatic dibasic acids are simply referred to as dibasic acids), ethylene glycol, propylene glycol, 1, 4-butanediol, neopentyl glycol, 1,5-pentanediol, spiroglycol, 1,6-hexanediol,
A resin derived from a diol compound such as bis (β-hydroxyethyl) terephthalate as a raw material, and having a number average molecular weight of less than 10,000, more preferably less than 5,000, is a preferable example.

The above-mentioned polyether polyester having a carboxyl group or a hydroxyl group as an end group is a diol compound represented by diethylene glycol, dipropylene glycol, triethylene glycol, tripropylene glycol, tetramethylene glycol or tetraethylene glycol, Examples thereof include resins derived from the dibasic acids and polyether compounds represented by polyethylene glycol ether, polypropylene glycol ether, and polytetramethylene glycol ether, the number average molecular weight of which is 10,000 or less, preferably 50.
Those within 00 are preferable examples.

When the lactic acid resin is a macromonomer of the present invention derived from a lactic acid block copolymer resin (defined in C above), Y in the formula 1 is D type, L type, D / L composite type. Any of polylactic acid, polyhydroxycarboxylic acid other than polylactic acid, polyaminocarboxylic acid, polymercaptocarboxylic acid, polyester having a terminal functional group of a carboxyl group or a hydroxyl group, polyether having a terminal functional group of a carboxyl group or a hydroxyl group One or two second copolymer resin components selected from polyesters are used as raw materials, respectively, and polycondensed in a one-step or two-step reaction to obtain a polymer composed of repeating units of lactic acid and a polymer. Two
The copolymer resin component is a monovalent block polymer contained as a constitutional unit, and is defined as a monovalent lactic acid block copolymer resin group in the present invention.

The above-mentioned polyhydroxycarboxylic acid is ε-
It is represented by a caprolactam ring-opening adduct, polyhydroxyacetic acid, polyhydroxypropionic acid and the like.

The above-mentioned polyaminocarboxylic acid is D /
L-alanine polymer and poly-11-aminoundecanoic acid,
Typical examples thereof include poly-12-aminododecanoic acid and polyamide resins having a carboxyl group or an amino group at one end.

The above-mentioned polymercaptocarboxylic acid is represented by polymercaptoacetic acid and polymercaptopropionic acid.

As a method for more specifically obtaining the macromonomer of the present invention, although not particularly limited, the following production methods 1 to 3 are preferable.

The first manufacturing method is a method using (A) polylactic acid as a raw material, and is represented by the following (A) to (D).

As a method of producing (a), a stoichiometric amount of glycidyl (meth) acrylates is allowed to act on a carboxyl group at one end of polylactic acid, and one end of (meth) polylactic acid is added. A method of introducing an acryloyl group.

As the method (b), a low molecular weight monomer having an isocyanate group and an ethylenic double bond is allowed to act on the terminal hydroxyl group of polylactic acid in a stoichiometric amount to give polylactic acid (A 1), a method of selectively introducing a polymerizable functional group of any one of (meth) acryloyl group and isopropenyl group to one end.

As the method (c), methacrylic acid or acrylic acid is allowed to act on the hydroxyl group at one terminal of polylactic acid in a stoichiometric amount, and one is added to one terminal of polylactic acid.
A method of introducing an acryloyl group.

As the method (d), an unsaturated dibasic acid anhydride such as maleic anhydride or itaconic anhydride is allowed to act on the hydroxyl group at one end of polylactic acid to give one end of polylactic acid (A). A method of introducing a maleyl group or a fumar group into

The second production method is a method in which (B) lactic acid random copolymer resin is used as a raw material, and the above (A) to (D) are used.
It is represented by the same method except that the polylactic acid raw material shown in 1 above is a lactic acid random copolymer resin, and the following method (e).

As the method (e), a glycidyl (meth) acrylate or an isocyanate group-containing low molecular weight monomer is added to a lactic acid random copolymer resin having a mercapto group or an amino group at one end at room temperature to 120 ° C. , And finally 1 at one end of the lactic acid random copolymer resin
And a method of selectively introducing a polymerizable functional group of any one of a (meth) acryloyl group and an isopropenyl group.

The third production method is the same as the first or second method except that the lactic acid block copolymer resin (C) is used.

Although not particularly limited, in the first to third production methods, the reaction conditions of the lactic acid resin [I] and the low molecular weight monomer [II] are appropriately set in an inert solvent. And preferably under an inert gas atmosphere such as in a nitrogen stream and without solvent, or for example toluene, benzene, xylene, methyl chloride, methylene chloride, trichloroethane, trichloroethylene, diphenyl ether, anisole, etc. It may be diluted with a solvent using the above solvent.

The lactic acid resin [I] and the low molecular weight monomer [I]
In the reaction with I], the following known reaction catalysts and reaction cocatalysts include, for example, metal tin powder catalysts, stannous octoate, dibutyltin dilaurate, dibutyltin dioxide, and other organotin catalysts, Phosphite catalyst, orthotitanate-n-butyl, orthotitanate-n
-Organic titanium-based catalysts such as isopropyl may be appropriately present, and there is no particular limitation.

Further, when the lactic acid-based resin [I] is obtained in advance, there is no particular limitation, and D / L lactic acid, D / L lactic acid alkyl ester, cyclic lactide or the like and the second copolymerization are carried out in an inert solvent. The component or the second component resin for block copolymer is usually at 80 to 200 ° C., preferably 110 to 15
A method obtained by carrying out a polycondensation reaction at a reaction temperature of 0 ° C. can be preferably adopted.

Further, the cocatalyst and reaction conditions used for introducing and reacting an acryloyl group, a methacryloyl group or an isopropenyl group as a polymerizable functional group at one end of the lactic acid resin [I] or its precursor resin are already known. The method may be adopted and there is no particular limitation. Generally, for the purpose of completing the reaction at a low temperature in a short time, for example, in the reaction of a carboxyl group and a glycidyl group, a tertiary amine or a salt thereof is used in a very small amount as a reaction catalyst, or a hydroxyl group and an isocyanate are used. The reaction may be carried out by using a small amount of the above-mentioned organotin catalyst or tertiary amine as a reaction catalyst.

Further, the polymerization reactivity of the unsaturated group of the macromonomer of the present invention (hereinafter referred to as PLA macromonomer) is determined by the ethylenic unsaturation of the usual (meth) acryloyl monomer or isopropenyl monomer. It exhibits substantially the same polymerization characteristics as the group and the like, and exhibits excellent copolymerizability with one or more of the following unsaturated monomers (hereinafter referred to as ethylenically unsaturated monomers).

Examples of the ethylenically unsaturated monomer include:
Vinyl acid monomers such as vinyl acetate, vinyl formate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl laurate, vinyl stearate, vinyl benzoate, isopropenylacetic acid; ethylene, propylene, 1-butene, isobutene. Olefin monomers, acrylic acid and its salts; methacrylic acid and its salts; methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, 2-ethylhexyl methacrylate,
(Meth) acrylic acid esters such as 2-ethylhexyl acrylate, stearyl methacrylate, stearyl acrylate, dodecyl methacrylate, dodecyl acrylate, octadecyl methacrylate, octadecyl acrylate; typified by hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate (Meth) acrylic acid hydroxyesters; (meth) acrylic acid glycidyl esters represented by glycidoxymethacrylate and glycidoxyacrylate; acrylamide, methacrylamide, N-methylacrylamide, N-ethylacrylamide, N, N -Acrylamides such as dimethyl acrylamide and diacetone acrylamide and their Or quaternary salts, N-methylol acrylamides; unsaturated dibasic acids such as maleic acid, fumaric acid, maleic anhydride, fumaric anhydride, and itaconic acid, and salts or ester derivatives thereof; maleimide, phenylmaleimide, benzylmaleimide Unsaturated imides such as styrene; α-methylstyrene, vinylphenol, isopropenylbenzene, and aromatic unsaturated monomers such as isopropenylphenol; nitriles such as acrylonitrile and methacrylonitrile; vinyl chloride, vinylidene chloride, fluorine Vinyl halides such as vinyl chloride and vinylidene fluoride; allyl compounds such as allyl acetate and allyl chloride; vinyltrimethoxysilane, vinyltriethoxysilane, vinyldimethoxymethylsilane, vinyldiethoxymethylsilane, acryloylpropio Vinylsilanes such as xytrimethoxysilane, acroylpropyltriethoxysilane, acryloylpropoxydimethoxymethylsilane, acroylpropyldiethoxymethylsilane, vinylhydrogensilane; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether Such as vinyl ethers; methacrylamidopropane sulfonic acid and its salts; methacrylamidopropyl dimethylamine and its salts and quaternary salts; mono-substituted phosphoric acid esterification products of hydroxy (meth) acrylate, etc., and one or two of them. The above is used.

Among the above, (meth) acrylic acid esters and / or styrene, α-methylstyrene, acrylonitrile, ethylene, propylene and vinyl acetate are particularly preferable examples.

The PLA macromonomer of the present invention also exhibits polymerizability itself.

The PLA macromonomer of the present invention can be copolymerized with the above-mentioned ethylenically unsaturated monomer to induce it into a characteristic polymer. It is characteristic that it is useful as a high-level modifier that can impart hydrolyzability.

Particularly, the PLA macromonomer of 0.1 to 90 is used.
10 to 9% by weight of the above ethylenically unsaturated monomer
A copolymer derived from 9.9% by weight is particularly preferable because it has a high compatibility effect with various plastics or an alloying agent effect.

A polymer characterized by being graft-modified with another polymer in the range of 1 to 50% by weight of the PLA macromonomer is a polymer having a porous structure when alkali hydrolyzed. The polymer of the present invention is most useful because it can be made into a united body, and the polymer having a porous structure can be preferably developed for applications such as a breathable film and a separation membrane material.

That is, the polymer of the present invention means a PLA macromonomer homopolymer, or at least 0.1% by weight of PLA macromonomer in terms of PLA macromonomer structural unit, or 1% by weight in order to exert the characteristics more. %
Above, particularly preferably a polymer copolymerized in the range of 5 to 90% by weight, in a preferred embodiment from the fact that it has the property of microbial disintegration and appropriately retains the alkali hydrolyzability. is there.

The other polymer is polypropylene resin,
Polyethylene resin, polycarbonate resin, ABS resin (acrylonitrile-butadiene-styrene copolymer resin), polylactic acid molding resin, polycaprolactone resin,
General-purpose engineering thermoplastics such as polyester resin, acrylic resin, polyester urethane resin, polyimide resin, polystyrene resin, vinyl chloride resin, vinylidene chloride resin, ionomer resin, vinyl acetate resin, polyvinyl butyral resin, polyvinyl alcohol resin, and other natural rubber Typical are hot-melt resins and resin compositions thereof.

The other polymers include epoxy resin, urethane resin, urea resin, urea-melamine resin, melamine resin, urea-phenol resin, phenol resin, xylene resin, unsaturated polyester resin, unsaturated acrylic resin, various types. A thermosetting polymer resin represented by a reactive hot melt resin and an allyl resin is also included.

The environment for obtaining the polymer of the present invention is not particularly limited, and solution polymerization, bulk polymerization, polymerization in an aqueous solution (suspension polymerization or emulsion polymerization, etc.), thermal polymerization using a radical initiator, photoinitiation. Polymerization, radiation polymerization,
It may be achieved by employing known polymerization means such as cationic polymerization.

The radical polymerization method is not particularly limited, but an active radical is generated by using a known radical initiator or photosensitizer (also referred to as a photoinitiator) in an inert atmosphere such as a nitrogen stream. It is a general method to do it once it occurs,
Examples of such a radical initiator include 2,2′-azobisisobutyronitrile and 2,2′-azobis (4-
Methoxy-2,4-dimethylvaleronitrile), 1,
Azo initiators such as 1′-azobis (cyclohexyl-1-carbonitrile) and dimethyl-2,2′-azobis (2-methylpropionate), benzoyl peroxide,
Lauroyl peroxide, di-n-propyl dicarbonate,
There are peroxide initiators such as cumene hydroperoxide, acetyl peroxide and the like. A photosensitizer is used in the photoinitiated polymerization, and examples of the photosensitizer include benzoin ethers, benzoin ethyl ethers, and acetophenone.

When the polymer of the present invention is obtained in an aqueous solution, a radical initiator such as ammonium persulfate, the photosensitizer, a water-soluble azo initiator, etc. may be used. Further, in the case of obtaining the polymer obtained by grafting of the present invention, it may be achieved by using the above-mentioned peroxide initiator and the like, if necessary, and there is no particular limitation.

In the cationic polymerization, a known Friedel-Crafts catalyst may be used, or a cationic photoinitiator such as iodonium salt of borofluoric acid may be used.

In solution polymerization, for example, benzene, toluene,
Xylene, mineral spirits, Solvesso # 100,
Solvesso # 150, methanol, ethanol, butanol, isopropanol, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, tetrahydrofuran, dioxane, n-hexane,
n-heptane and other dibutyl phthalate, di-phthalate
A phthalate ester plasticizer such as n-octyl, glycerin triacetate (also known as triacetin) and the like may be used. The polymerization temperature is appropriately determined depending on the polymerization method, but is generally -20 ° C to 180 ° C, preferably -1.
The range of 0 ° C to 150 ° C, particularly preferably 0 ° C to 130 ° C is preferable. Further, a known molecular weight adjusting agent may be used at the time of polymerization, or a heat antiaging agent, an ultraviolet absorber, an ultraviolet stabilizer, a metal ion deactivator or the like may be added after the completion of the polymerization.

The polymer of the present invention has the properties of the PLA macromonomer and / or the properties of the ethylenically unsaturated monomer as appropriate, and at least 70% of the PLA macromonomer homopolymer or the PLA macromonomer is used.
~ 90 wt% and 30 ~ 10 wt% of ethylenically unsaturated monomer, the random copolymer is relatively stable to acidic water and normally has polystyrene-like hardness and mechanical properties. A polymer that exhibits strength is characteristic and preferable.

On the other hand, at most 1 PLA macromonomer
˜70 wt% and 30 to 99 wt% or more of the ethylenically unsaturated monomer, the random copolymer shows extremely excellent stability against water and durability under neutral or acidic conditions and biodegradability. It is characteristic and preferable that it exhibits the property of being extended for an arbitrary period and exhibits the property of expanding the compatibility range with various plastics to a higher range.

Therefore, the polymer of the present invention is a polymer of the PLA macromonomer alone of the present invention or a PLA macromonomer of the present invention and an arbitrary amount of an ethylenically unsaturated monomer, depending on the purpose of modifying plastics. The copolymer may be selected and used, and the specific use of the polymer is not limited.

The polymer of the present invention is an additive aid for improving alloying properties of plastics (various resin compatibilizers, etc.).
, Use as a microbial degradability-imparting agent for plastics, Use as an alkali hydrolyzability imparting agent for plastics, Use as a microbial collection or localizing agent, Porous body by microbial or alkali hydrolysis action Applications for manufacturing, adhesives, adhesives, adhesive-adhesive migration adhesives, coatings for plastics and metals,
Applications for paper inks, thermal transfer binders, water-based inks, unsaturated polyester shrinkage reducing agents,
It can be preferably used for applications such as unsaturated polyester resin applications or auxiliary agents for improving dispersibility of fillers, applications as epoxy resin functional improving agents or latent curing agents. In particular, it is useful as a compatibilizing agent for multi-component plastics and for producing a porous body by the action of microorganisms or alkali hydrolysis.

[0103]

EXAMPLES In order to further clarify the present invention, examples will be described below, but the present invention is not specified or limited in any way, and parts or% other than those specifically mentioned are parts by weight or% by weight, respectively. .

Comparative Example 1 (US) Polystyrene macromonomer having a weight-average molecular weight of 13,000 and having a methacrylate terminal at one end, which is commercially available from ARCO Chemical Co., Ltd. (trade name: Chemlink # 4)
500 "(2-polystyrylethylmethacrylate) in toluene solution with ethylenically unsaturated monomer,
When 1% of azobisisobutyronitrile is used together, the radical polymerizability at a concentration of 50% in terms of solid content and the polymerizability of itself, and after forming a film with a thickness of 100 μm, weigh 0.5 gr Collected and biodegradable and 1
The change in hydrolysis weight when immersed in N-alkaline water was examined, and the results are shown in Table 1. In the table, Chemlink # 45
The macromonomer of 00 was described as PS.

The homopolymer using this macromonomer and the copolymer of butyl methacrylate and Chemlink macromonomer 25% are 100 to 150 ° C./1.
It was found that the heat stability after 0 hours had no problem with the weight change being negligible.

Comparative Example 2 Polymethylmethacrylate macromonomer having a weight-average molecular weight of about 4,700 and solid at room temperature and containing a methacrylate group at one end "commercial name: KM-50", which is commercially available from Kyowa Gas Chemical Industry Co., Ltd. In a toluene solution with an ethylenically unsaturated monomer, when used together with 1% of azobisisobutyronitrile, the radical polymerizability at a solid content conversion charged concentration of 50%, and the polymerizability of itself, Thickness 100 μm
After forming into the film of No. 1, 0.5 gr was weighed and collected, and the results of examining the microbial degradability and the change in hydrolysis weight when immersed in 1N-alkaline water are shown in Table 1. In the table, K is the polymethylmethacrylate macromonomer.
It is indicated as M.

Comparative Example 3 A polyacrylonitrile macromonomer "trade name: AN-4" containing a methacrylate at one end and solid at room temperature, which is commercially available from Toagosei Co., Ltd., was obtained and was mixed with an ethylenically unsaturated monomer. When used together with 1% azobisisobutyronitrile in a toluene solution, it has radical polymerizability at a solid content of 50%, and its own polymerizability, thickness 100 μm.
After being formed into a film of No. 1, 0.5 gr of the film was weighed and collected, and the results of examining the microbial degradability and the change in hydrolysis weight upon immersion in 1N-alkaline water are shown in Table 1. In the table, the acrylonitrile macromonomer is indicated as AN.

Comparative Example 4 With respect to a liquid resin obtained by adding 30 mol of propylene oxide to 1 mol of butanol, methacrylic acid isocyanatopropoxy ester was used as an isocyanate methacrylate in the same amount as 1 equivalent of one terminal hydroxyl group of the resin. In the presence of 0.01% of methylhydroquinone and 0.005% of dibutyltin dilaurate, while allowing dry air to blow into the system, the reaction was carried out at 50 ° C. for 10 hours to introduce a methacryloyl group at one terminal at room temperature. A polyether macromonomer having a weight average molecular weight of about 1800 was obtained. The copolymerizability with an ethylenically unsaturated monomer and the microbial degradability by itself which were carried out in the same manner as in Comparative Example 1 are shown in Table 1.
It was described in 1. In addition, a homopolymer using this macromonomer or a 50% copolymer with methyl methacrylate tends to undergo air oxidation deterioration and hydrolysis under heat, and is subjected to heat treatment at 100 to 150 ° C. for 10 hours in air. A marked decrease in molecular weight and discoloration were observed. In the table, the macromonomer was designated as P0.

Example 1 0.3% of metal tin powder as a catalyst and 1.5% of lauryl alcohol were charged to mixed lactic acid having the same D: L body ratio, and the mixture was mixed with a xylene solvent in a nitrogen stream. Reaction temperature 140 ℃,
By carrying out reflux reflux polycondensation of a solvent for 20 hours under 100 mmHg, the weight average molecular weight of one end hydroxyl group is 5,20.
0 (polystyrene-equivalent molecular weight obtained by GPC measurement) of medium molecular weight polylactic acid was obtained. Further, 500 parts of the solution is taken as a 50% solution of tetrahydrofuran solvent which has been dehydrated in advance, set at 110 ° C., and then 15 parts of isocyanate ethyl methacrylate (MW = 155) containing 0.1% of methylhydroquinone is passed through dry air. Was added and reacted in the presence of 0.005% of dibutyltin dilaurate for 5 hours. Finally, the solvent was removed to obtain a light yellow crystalline solid PLA macromonomer (PLA-50A) having a methacrylate urethane group introduced at one end at room temperature.

The glass transition temperature of PLA-50A was approximately 52 ° C. In addition, in a toluene solution of PLA-50A and an ethylenically unsaturated monomer, when 1% of azobisisobutyronitrile is used in combination, the radical polymerizability at a solid content converted 50% concentration and the polymerizability of itself, Thickness 100μ
After being formed into a film of m, 0.5 gr of the film was weighed and sampled, and the results of examining the microbial degradability and the change in hydrolysis weight upon immersion in 1N-alkaline water are shown in Table 1.

Example 2 PLA precursor polymer 50 obtained in the same manner as in Example 1
To 0 part, 19.5 parts of p-isopropenyl-α, α′-dimethylbenzyl isocyanate (MW = 201) was reacted in the same manner as in Example 1 to give an isopropenyl group introduced at one end at room temperature. A PLA macromonomer (PLA-50B) was obtained as a yellow crystalline solid.

The glass transition temperature of PLA-50B was approximately 52 ° C. Further, in a toluene solution of PLA-50B and an ethylenically unsaturated monomer, when 1% of azobisisobutyronitrile is used in combination, the radical polymerizability at a solid content conversion charged concentration of 50% and the polymerizability of itself, Thickness 100μ
After being formed into a film of m, 0.5 gr of the film was weighed and sampled, and the results of examining the microbial degradability and the change in hydrolysis weight upon immersion in 1N-alkaline water are shown in Table 1.

Example 3 0.05 part of stannous octoate as a catalyst, 175 parts of L-lactide, 40 parts of L-lactic acid and 500 parts of anisole as a solvent were charged, and a nitrogen stream was supplied at a reaction temperature of 145 ° C. The ring-opening polycondensation reaction was carried out for 15 hours. Add 25 parts of mercaptopropionic acid to the same system, and add 3-4 parts.
The dehydration polycondensation was continued for an hour. As a result of this operation, the solvent was finally removed to obtain a lactic acid random copolymer resin having a mercapto group and a carboxyl group at one end, and the weight average molecular weight thereof was 2,950 (polystyrene-equivalent molecular weight obtained by GPC measurement). )Met. Furthermore, to 500 parts of this, 2 of glycidoxymethacrylate (MW = 142)
4 parts were reacted at 120 ° C. for about 18 hours, and a terminal methacryloyl group-introduced PLA macromonomer: PLA-
30C was obtained.

The glass transition temperature of PLA-30C is about 60.
It was ℃.

Further, in a toluene solution of PLA-30C and an ethylenically unsaturated monomer, when 1% of azobisisobutyronitrile was used in combination, the radical polymerizability at a solid content conversion 50% concentration and the polymerization of itself. Table 1 shows the results of examining the microbial degradability and the change in hydrolysis weight when immersed in 1N-alkaline water after weighing and collecting 0.5 gr of the film after molding into a film having 100 μm in thickness and 100 μm in thickness.

Example 4 Using 3% of metal tin fine powder as a catalyst, L-type lactic acid and a small amount of isostearyl acid were made to coexist to form a 50% solution of anisole as a solvent, and the reaction temperature was 145 ° C. in a nitrogen stream for 15 minutes.
The dehydration polycondensation reaction was performed over time. Separately prepared in the same system, 0.2 mol of hydroxypropionic acid, 0.5 mol of terephthalic acid, 0.4 mol of adipic acid and 1,
A polyester oligomer having a weight average molecular weight of 1,950, wherein the terminal functional groups derived from 0.6 mol of 3-propylene glycol and 0.3 mol of 1,4-butanediol are hydroxyl groups and carboxyl groups. 25 parts was added and dehydration polycondensation was continued for 10 hours. As a result of this operation, the solvent was finally removed to obtain a lactic acid block copolymer resin having a carboxyl group at one end in one molecule, and the weight average molecular weight thereof was about 11,000 (polystyrene obtained by GPC measurement). It was the converted molecular weight). Furthermore, to this 500 parts, glycidoxymethacrylate (MW =
Then, 6.5 parts of 142) was reacted at 120 ° C. for about 12 hours to obtain a PLA macromonomer having a terminal methacryloyl group introduced: PLA-110C.

The glass transition temperature of the resin component of PLA-110C based on polylactic acid was about 60 ° C. as a result of viscoelastic behavior analysis (TBA measurement).

Further, in a toluene solution of PLA-110C and an ethylenically unsaturated monomer, when 1% of azobisisobutyronitrile was used in combination, the radical polymerizability at a concentration of 50% as solid content and the polymerization of itself. Table 1 shows the results of examining the microbial degradability and the change in hydrolysis weight when immersed in 1N-alkaline water after weighing and collecting 0.5 gr of the film after molding into a film having 100 μm in thickness and 100 μm in thickness.

Example 5 A lactic acid block copolymer resin 50 having a hydroxyl group at one end, which was obtained in the same manner as in Example 4 except that isostearic acid was replaced with isostearyl alcohol.
To 0 part, 4.5 parts of maleic anhydride (MW = 98) was caused to act in the same manner as in Example 1 to obtain PLA-110D. The results of examining the polymerizing behavior and biodegradability of this product are shown in Table 1.

Example 6 A mixed solution containing 3% of fine metal tin powder as a catalyst, 20% of D / L mixed lactic acid, and 77% of anisole as a solvent was placed in a nitrogen stream at a reaction temperature of 145 ° C. / 150 mm
The dehydration polycondensation reaction was carried out under Hg for 15 hours. 10 parts of polypropylene glycol monobutyl ether having a molecular weight of 1000 was added to the same system to continue the reaction, and finally a precursor having a weight average molecular weight of about 3,300 in which one end group was sealed and stabilized was obtained.

Further, with respect to the solid content of 500 parts of the precursor of the same system, 30.5 parts of p-isopropenyl-α, α'-dimethylbenzylisocyanate (MW = 201) was treated in the same manner as in Example 1. Then, PLA-330E was obtained. P
The glass transition temperature of the polylactic acid portion of LA-330E is about 5
It was 0 ° C.

Further, in a toluene solution of PLA-330E and an ethylenically unsaturated monomer, when 1% of azobisisobutyronitrile was used in combination, the radical polymerizability at a solid content of 50% concentration and the polymerization of itself. After being formed into a film of 100 μm in thickness and 100 μm in thickness, 0.5 gr of the film was weighed and sampled, and the biodegradability and the change in hydrolysis weight upon immersion in 1N-alkaline water were examined, and the results are shown in Table 1.

[0123]

[Table 1] Explanation of symbols: MMA; methyl methacrylate, BA; acrylic acid-n
-Butyl AN; Acrylonitrile present; Radical copolymerizable ◎; If the change in weight (reduction rate) is as good as 50 to 100% as a result of the buried biodegradability test after 1 month, or 1N
-If the morphology disappears within 2 hours in the alkaline water immersion test, the result of the buried microbial degradability test after 1 month shows a good weight change of 10 to 50%, or in the 1N-alkaline water immersion test. When the morphology disappeared within 10 hours Δ: When the result of the buried microbial degradability test after 1 month showed a weight loss of 5 to 10%, or in the 1N-alkaline water immersion test, there was only a slight deformation within 24 hours or When swelling was observed: When the result of the buried microorganism degradability test after 1 month showed almost no weight loss, or when no deformation was observed in 24 hours in the 1N-alkaline water immersion test.

However, as the soil and environment used for the buried microbial degradability test, soil in which deciduous leaves had accumulated and turned into mulch soil was sampled from a neighboring site, and the soil environment was maintained.

Example 7 15 parts of PLA-50A obtained in Example 1, 10 parts of acrylonitrile, 75 parts of styrene, 200 parts of methyl ethyl ketone and 200 parts of t-butanol as a solvent,
Furthermore, 0.5 of azobisvaleronitrile as a polymerization initiator
Was used for 5 hours at 75 ° C. in a nitrogen stream, and the remaining monomer was polymerized as 0.2 part of azobisvaleronitrile for 3 hours. Then, the solvent was removed under reduced pressure while raising the temperature to 130 to 150 ° C. to obtain a polymer containing PLA-50A.

A 10 cm square film obtained by forming the polymer containing PLA-50A into a film having a thickness of 50 μm by hot pressing at 125 ° C. was heated to 50 ° C. and heated to 0.2.
The film was immersed in a N-sodium hydroxide solution for 2 hours, washed with water, and dried at room temperature. As a result, the film was a film showing gas-permeable properties although water droplets could not easily pass through. As a result of observation with a scanning electron microscope, fine holes with a maximum diameter of 0.1 μm or less were present.

Example 8 P having an intrinsic viscosity of 0.3 obtained in the same manner as in Example 7 except that styrene was replaced by -n-butyl acrylate.
A polymer containing LA-50A was blended with 5 to 10% of a polymer prepared separately, to a crystalline D-type polylactic acid resin having a weight average molecular weight of 100,000 in terms of polyethylene measured by GPC, and further prepared separately. 10 to 5 of poly (2-ethylhexyl acrylate) -based thermoplastic acrylic rubber having a weight average molecular weight of 60,000 in terms of polyethylene measured by GPC
As a result of adding and mixing 0%, the micro dispersion stability of the thermoplastic acrylic rubber was secured, and the impact resistance of the polylactic acid resin was significantly improved.

In this example, the result of the simple polymer blend of the D-type polylactic acid resin and the thermoplastic acrylic rubber when the PLA-50A graft polymer was not used was as follows.
There was no compatibility, the matrix thermal stability was lacking, and the effect of improving mechanical strength was hardly exhibited.

Example 9 5 parts of PLA-50B obtained in Example 2, 95 parts of α-methylstyrene, 200 parts of toluene as a solvent and t-
Using 200 parts of butanol and 1 part of benzoyl peroxide as a polymerization initiator, 85 parts in a nitrogen stream was used.
Polymerization was carried out at 5 ° C. for 5 hours, and the remaining monomer was polymerized with 0.2 part of benzoyl peroxide for 3 hours. Then 130
The solvent was removed under reduced pressure while raising the temperature to ˜150 ° C. to obtain a polymer containing PLA-50B.

8% of the polymer containing PLA-50B and D /
As a result of polymer blending 35% of the L-type polylactic acid resin with a thermoplastic polystyrene resin in nitrogen at 180 ° C., a polystyrene-modified resin in which the polylactic acid resin was microdispersed and stabilized was obtained.

In this example, the result of the simple polymer blend of the D / L-type polylactic acid resin and the thermoplastic polystyrene resin in the case where the PLA-50B graft polymer was not used showed no dispersion stability. It was

[0132]

The macromonomer of the present invention is used in Examples 1 to 6
As is clear from the above, it exhibits microbial degradability and alkaline hydrolyzability, and is highly copolymerizable with various ethylenically unsaturated monomers, and its polymer is clear in Examples 8 and 9. As described above, it was proved that it is highly practical as a polymer compatibilizer. That is, it is possible to easily achieve the addition of functionalities such as microbial disintegration and alkali hydrolysis as properties that must be possessed to realize environmental measures and pollution-free needs of already known various thermoplastics. It can be mentioned as a characteristic effect.

On the other hand, when the macromonomer according to the present invention was disintegrated by a microorganism, the decomposition products were mainly water and carbon dioxide gas. Similarly, the alkaline water hydrolysis product of the macromonomer alone was found to be a monomer composed mainly of lactic acid, and was a macromonomer with high pollution-free property.

Further, as is clear from the results of Example 7, the polymer obtained by using the macromonomer of the present invention can easily produce a polymer molded product having an excellent porous structure, and is suitable for various types of gas permeation. It has also been found that it will be a technology that facilitates the provision of a functional polymer material.

As shown in Comparative Examples 1 to 4, the conventional macromonomers have high copolymerization reactivity with various unsaturated monomers, but have no microbial disintegration property and alkali hydrolyzability. The macromonomer had a different property.

Claims (9)

[Claims] 1. [I] The weight average molecular weight is 1,000 to 5.
Polylactic acid derived from (A) lactic acid and / or cyclic lactide in the range of 10,000, and selected from (B) lactic acid and / or cyclic lactide, mercaptocarboxylic acid, hydroxycarboxylic acid other than lactic acid, aminocarboxylic acid, etc. A lactic acid random copolymer resin derived from
And (C) polylactic acid, polymercaptocarboxylic acid,
A lactic acid content derived from polyhydroxycarboxylic acid derived from hydroxycarboxylic acid other than lactic acid and one selected from polyaminocarboxylic acid as a raw material is 30 to
95% by weight of any of the lactic acid block copolymer resins and [II] selected from the group consisting of isocyanate groups, glycidyl groups, acid anhydride groups, amide groups, carboxyl groups and hydroxyl groups having a molecular weight of 500 or less. A macromonomer represented by the following formula 1, which is derived from a low-molecular monomer having one functional group and an ethylenic double bond at the same molecular end. [Chemical 1] (In the formula, X is a hydroxyl group which is a terminal functional group of [I],
One functional group selected from a carboxyl group, an amino group, a mercapto group and the like and one functional group selected from the group consisting of an isocyanate group [II], a glycidyl group, an acid anhydride group, a carboxyl group and a hydroxyl group. Y is a bonding group formed by chemically reacting with a group, and Y is a monovalent polylactic acid group remaining after removal of the terminal functional group of [I] involved in the reaction with [II], and random copolymerization of lactic acid. A resin group or a lactic acid block copolymer resin group, wherein R ¹ is hydrogen or a methyl group, R ² is hydrogen, a carboxyl group or a carbon number of 1 to 20.
Means an alkyl ester group. ) 2. A weight average molecular weight of 1,000 to 20,0.
In the range of 00, a low molecular weight monomer having an isocyanate group and an ethylenic double bond or a carboxyl group and an ethylenic diamine are used as [II] for [I] having a hydroxyl group or an amino group as a terminal functional group. Characterized by reacting a low molecular weight monomer having a heavy bond with the hydroxyl group or amino group of [I] and the isocyanate group or carboxyl group of [II] at a reaction molar equivalent ratio of about 1: 1. The macromonomer according to claim 1, wherein 3. A weight average molecular weight of 1,000 to 20,0.
In the range of 00, a low molecular weight monomer having a hydroxyl group and an ethylenic double bond or a glycidoxy group and an ethylenic double bond as [II] for [I] having a carboxyl group as a terminal functional group. With a low molecular weight monomer having a molar ratio of about 1: in the reaction group of the carboxyl group of [I] and the hydroxyl group or glycidoxy group of [II].
The macromonomer according to claim 1, which is obtained by reacting with 1. 4. The weight average molecular weight of [I], wherein one end carboxyl group is alkyl esterified with a higher alcohol or one end hydroxyl group is halide treated with an alkyl halide.
1 or 2 selected from the group consisting of polylactic acid of 1), polyhydroxycarboxylic acid excluding polylactic acid, polyaminocarboxylic acid, polyester having a carboxyl group or hydroxyl group at one terminal, and polyether polyester having a carboxyl group or hydroxyl group at one terminal. The macromonomer according to any one of claims 1 to 3, which is a lactic acid block copolymer (C) derived from one or more kinds of resins. 5. A compound represented by formula 1 having a weight average molecular weight of 1,
Macromonomer according to any of claims 1 to 4, in the range of 200 to 10,000. 6. The macromonomer of the formula 1 according to claim 1 in an amount of 0.1 to 90% by weight and one or more kinds of other unsaturated monomers copolymerizable with the macromonomer 99.9. ~ 1
A polymer characterized by being copolymerized with 0% by weight. 7. A polymer obtained by grafting the macromonomer of the formula 1 according to claim 1 to another polymer in a range of 1 to 50% by weight. 8. The polymer according to claim 6 or 7 is processed into a thread-like or film-like shape and then alkali-hydrolyzed to form a fine porous structure, and the processed product is a breathable film and a breathable film. The method for using the polymer according to claim 6 or 7, which is used for producing a non-woven fabric. 9. The method for using the polymer according to claim 6, wherein the polymer according to claim 6 is used as a polymer alloying agent or a compatibilizing aid.