JP3426057B2 - High acid value lactone polymer and method for producing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a lactone polymer which is highly branched and has a high acid value. More specifically, it can be widely used for adhesives, adhesives, cured materials, polymer plasticizers, polyamide resin modifiers, compatibilizers, paints, alkaline water dispersible binders, inks, biodegradable applications and medical applications. It relates to a high acid value lactone polymer.

[0002]

BACKGROUND OF THE INVENTION The present inventor has found that the number of molecules in a molecule is 10-5,000.
Polymer (A) having a number of hydroxyl groups is used as an initiator,
By addition-polymerizing a lactone monomer, a lactone polymer (B) having a high hydroxyl value, which is flexible and rich in processability and has a large number of hydroxyl groups in the molecule, was developed. This one is an adhesive,
It can be used for various applications such as adhesives, paints, cured molding materials, and polymer plasticizers.

[0003]

However, among these applications, there is room for improvement in terms of function because the lactone polymer terminal is a hydroxyl group. To give specific examples of such uses, when added for the purpose of imparting flexibility and low shrinkage of the epoxy resin,
When the terminal is a hydroxyl group, the reaction with the epoxy group is slow, and sufficient flexibility and low shrinkage may not be exhibited. Further, when it is used for paints, when it has a hydroxyl group at the end, it is often not applicable to water-based paints because it has poor dispersibility in alkaline water. Further, when melt-kneading polyester or polycarbonate as a polymer plasticizer, a transesterification reaction may occur, and the mechanical strength of the molded product may decrease.

[0004]

Means for Solving the Problems As a result of intensive studies for solving the above problems of the high hydroxyl group lactone polymer (B), the present inventor has found that all of the hydroxyl groups of the high hydroxyl group lactone polymer (B) or We succeeded in introducing a carboxyl group into the terminal by reacting a part of it with an acid anhydride. Thereby, the above problems are not only all solved, but by introducing a carboxyl group at the terminal, for example, when used as a hot-melt adhesive between metals, the adhesive strength is remarkably improved, or the polyamide resin It was also found that the use as a modifier improves the prevention of coloration, heat stability and molding processability.

That is, the present invention is represented by the following general formula (1), and the number of moles of carboxyl group per 1 g of the polymer is 1 × 1.
0 ^{−4 to} 5 × 10 ⁻² mol, the number of carboxyl groups per molecule is 10 to 15,000, and the number average molecular weight is 20,0
It provides a high acid value lactone polymer characterized by being in the range of 0 to 2,000,000. Also,
Represented by the following general formula (2), the number of moles of carboxyl groups per 1 g of the polymer is 1 × 10 ^{−4 to} 5 × 10 ⁻² mol, the number of carboxyl groups per molecule is 10 to 15,000, and the number average molecular weight is Is in the range of 20,000 to 2,000,000, and a high acid value lactone polymer is provided. Furthermore, all or part of the hydroxyl groups of the high hydroxyl value lactone polymer represented by the following general formula (3) having 10 to 5,000 hydroxyl groups in the molecule are reacted with an acid anhydride. The present invention provides a method for producing the high acid value lactone polymer represented by the general formula (1). In addition, the polymer represented by the following general formula (4) having a carboxyl group of 10 to 1,000 in the molecule:
1 to 30% by weight, and lactone monomer 99.9 to 70
Mixture 1 consisting of weight% (total of 100% by weight of both)
The present invention provides a method for producing the high acid value lactone polymer represented by the general formula (2), which comprises melt-kneading 0.01 to 5 parts by weight of an acid catalyst with respect to 00 parts by weight.
Hereinafter, the present invention will be described in detail.

[0006]

[Chemical 5]

[0007]

[Chemical 6]

[0008]

[Chemical 7]

[0009]

[Chemical 8]

The high acid value lactone polymer represented by the general formula (1) of the present invention (hereinafter abbreviated as high acid value lactone polymer (C ₁ )) is basically 10 to 5 in the molecule. A polymer (A) having 000 hydroxyl groups is used as an initiator, and is produced by the reaction between the terminal hydroxyl group of a high hydroxyl value lactone polymer (B) obtained by addition polymerization of a lactone monomer and an acid anhydride. You can Further, the general formula (2) of the present invention
The high acid value lactone polymer represented by (hereinafter, abbreviated as high acid value lactone polymer (C ₂ )) is 10 to 1,0 in the molecule.
It can be directly produced by a method of addition-polymerizing a lactone monomer using a polymer having 00 carboxyl groups as an initiator.

The structures of the high acid value lactone polymers (C ₁ ) and (C ₂ ) of the present invention are represented by the general formula (1) or (2). L in both formulas is a structural unit of an arbitrary monomer having neither a hydroxyl group nor a carboxyl group, and is not limited to one type. Specifically, aromatic monomers such as styrene, methyl methacrylate, acrylonitrile, acrylic monomers such as acrylic acid, diene monomers such as butadiene, vinyl monomers such as vinyl acetate and vinyl chloride, ethylene Examples thereof include olefin monomers such as phenylene oxide and the like.

M in the general formula (1) is a monomer residue having a hydroxyl group in the molecule and is not limited to one kind. Specifically, vinyl alcohol monomer residues produced by saponification of vinyl acetate, 2-hydroxyethyl (meth) acrylate monomer residues, 2-hydroxypropyl (meth) acrylate monomer residues, 4 Examples thereof include a hydroxybutyl vinyl ether monomer residue.

T in the general formula (2) is a monomer residue having a carboxyl group in the molecule and is not limited to one kind. Specific examples thereof include a (meth) acrylic acid monomer residue and a maleic anhydride monomer residue.

In the formula, a, b, c, d, e, f, n ₁ and n ₂ represent the average degree of polymerization, and 0 ≦ a ≦ 1,000, 10
≦ b ≦ 5,000, 0 ≦ c ≦ 1,000, 0 ≦ d ≦ 1,
000, 10 ≦ e ≦ 1,000, 0 ≦ f ≦ 200, 2 ≦
The ranges are n ₁ ≦ 30 and 2 ≦ n ₂ ≦ 30. The above range is set on the assumption that the number of moles of carboxyl groups per 1 g of resin, the number of carboxyl groups per molecule, and the number average molecular weight are included in the above specified range. A in the case where the polymer (A) having 10 to 5,000 hydroxyl groups in the molecule, which is a raw material for producing the high acid value lactone polymer (C ₁ ) of the present invention, is a completely saponified or partially saponified polyvinyl alcohol, The range of b, c and n ₁ is 0 ≦ a
≦ 500, 100 ≦ b ≦ 5,000, 0 ≦ c ≦ 2,000
A range of 0 and 2 ≦ n ₁ ≦ 30 may be included in the above defined range.

R ^{1 in} both formulas is an alkylene group having 2 to 10 carbon atoms, and specific examples thereof include an ethylene group, a butylene group, a pentylene group, and a methylcapentylene group.
In the case of the most industrially useful ε-caprolactone, it corresponds to the pentylene group.

P in the general formula (1) is arbitrarily selected from a hydrogen atom (H) and a substituent represented by -OCO-R ^2- (COOH) _s . R ² has 2 to 20 carbon atoms (s
+1) represents a valent hydrocarbon residue, and s is an integer of 1 to 3. The structure of P has a high hydroxyl value lactone polymer (B)
It can be controlled by the kind and the addition ratio of the acid anhydride used for the reaction with respect to the hydroxyl group in the inside. That is, R ² and s are different depending on the type of acid anhydride. For example, for succinic anhydride R ² is CH ₂ CH ₂ , s = 1, for maleic anhydride R ² is CH═CH, s = 1, for phthalic anhydride R ² is C ₆ H ₄ ,
s = 1, the benzene tricarboxylic acid monoanhydride R ² is C ₆ H _3, s = 2 and benzene tetracarboxylic acid anhydride (benzene hydration of tetracarboxylic dianhydride) In R ²
Is C ₆ H ₂ , s = 3. Further, by adjusting the addition rate of the acid anhydride, -OCO-R ² and a hydrogen atom (H) -
The proportion of (COOH) _S can be controlled.

High acid value lactone polymer (resin) 1 of the present invention
The number of moles of carboxyl group per g is 1 × 10 ^{−4 to} 5 × 10.
^-2 mol, preferably 5 × 10 ^-4 to 2 × 10 ^-2 ,
More preferably, it is in the range of 8 × 10 ⁻⁴ to 1 × 10 ⁻² mol. The number of moles of the carboxyl group is 1 × 10 ^-4 mol
If it is less than 5, the amount of carboxyl group is small, and the advantage of having a carboxyl group in applications such as adhesives, cured materials, and coatings is lost. Conversely, if it exceeds 5 × 10 ^-2 mol, the lactone polymer It is not preferable because the properties, especially the flexibility and processability are lost and it becomes difficult to use for the above-mentioned applications. The number of moles of the carboxyl group can be easily determined by calculating a theoretical value, or by dissolving the sample in a solvent such as acetone and using a standard aqueous sodium hydroxide solution (or alcohol solution) to perform titration.

The number of carboxyl groups per molecule of the high acid value lactone polymer (C ₁ ) of the present invention is basically 1 to 3 times the number of hydroxyl groups in the high hydroxyl value lactone polymer (B) used. In the case of a high acid value lactone polymer (C ₂ ) using a raw material polymer having a carboxyl group in the molecule, the number of carboxyl groups in the above raw material polymer is equal to 10 to 15,
000, preferably 50 to 10,000, more preferably 100 to 5,000. In the high acid value lactone polymer (C ₁ ) or (C ₂ ), when the number of carboxyl groups is less than 10, the amount of carboxyl groups is small,
In applications such as adhesives, cured materials, paints, etc., the merits of having a carboxyl group are lost, and conversely, polymers having a number of more than 15,000 are not preferable because they are currently meaningless to manufacture. The number average molecular weight of the high acid value lactone polymer (C ₁ ) or (C ₂ ) of the present invention is 20,000 to
2,000,000, preferably 50,000-
1,000,000, more preferably 100,000-5
It is in the range of 0,000. The above molecular weight is 20,000
If less than, the balance between the amount of the carboxyl group and the addition amount of the lactone monomer is lost, the amount of the carboxyl group is reduced, or the properties as the lactone polymer, particularly the flexibility and molding processability are lost, which is not preferable. , Conversely 2,
If it exceeds, 000,000, the viscosity becomes too high, which causes problems such as deterioration of molding processability, which is not preferable. The above-mentioned number average molecular weight can be measured by using a known method for measuring the number average molecular weight, and in particular, a method using gel permeation chromatography (GPC) is the most simple and preferably used.

The high acid value lactone polymer of the present invention may have various forms depending on the number of lactone component chains, the degree of polymerization, the number of carboxyl groups, etc., from a colorless and transparent liquid to a transparent clay-like, wax-like, white crystalline solid. It has different physical properties such as reactivity and molding processability. Therefore, it is desirable to adjust the number, composition, and structure of carboxyl groups by controlling the raw materials, the composition of the feed, and the reaction conditions according to the application.

Further, the high acid value lactone polymer (C ₁ ) or (C ₂ ) of the present invention is used as a mixture with any substance such as an organic solvent, a polymerizable monomer, a curing agent, a catalyst and a stabilizer depending on the use. You can do it without any problems. Depending on the application, an unsaturated epoxy compound such as glycidyl (meth) acrylate, an unsaturated alcohol such as allyl alcohol or 2-hydroxyethyl (meth) acrylate, an acid modifier such as a tertiary amine or a metal ion may be added in an appropriate amount. It is also possible to modify all or part of the carboxyl groups.

Hereinafter, the high acid value lactone polymer (C
_The method for producing ₁ ) or (C ₂ ) will be described in more detail. The high acid value lactone polymer (C ₁ ) has ₁₀ to 5,0 in the molecule.
Using a polymer (A) having 00 hydroxyl groups as an initiator,
It is produced by reacting the terminal hydroxyl group of the high hydroxyl value lactone polymer (B) obtained by addition-polymerizing a lactone monomer with an acid anhydride.

The above-mentioned polymer (A) having 10 to 5,000 hydroxyl groups in the molecule is a completely or partially saponified polyvinyl alcohol, 2-hydroxyethyl methacrylate or the like, which is radically polymerizable in the molecule. Oligomers of compounds having both a double bond and a hydroxyl group, copolymers of these compounds with other radically polymerizable monomers, and graft modified products of these compounds to various polymers, hydrates of polydiene compounds, Examples include ethylene oxide modified products of polyamide, ethylene oxide modified products of polyphenol, polysaccharides, starch and cellulose. Among them, generally, a completely or partially saponified polyvinyl alcohol or a copolymer of 2-hydroxyethyl methacrylate and methyl methacrylate or styrene is preferably used. Further, as the lactone monomer to be subjected to addition polymerization using the polymer (A) as an initiator, methylated caprolactone such as ε-caprolactone and 4-methylcaprolactone, δ-valerolactone, β-propiolactone and two or more kinds of these Examples thereof include a mixture, and of these, ε-caprocactone, which is the most industrially useful, is preferably used.

Further, in the production of the above-mentioned high hydroxyl value lactone polymer (B), a ring-opening addition polymerization catalyst of a lactone monomer is generally used. Specific examples include inorganic bases, inorganic acids, organic alkali metal catalysts, tin compounds, titanium compounds, aluminum compounds, zinc compounds, molybdenum compounds and zirconium compounds. Above all,
A tin compound and a titanium compound are preferably used in terms of balance of ease of handling, low toxicity, reactivity, non-coloring property, stability and the like. Specific examples of the tin compound include stannous chloride, stannous octylate, monobutyltin oxide, monobutyltin compounds such as monobutyltin tris (2-ethylhexanate), dibutyltin compounds such as dibutyltin oxide, or titanium compounds. Examples thereof include tetrabutyl titanate and tetra-isopropyl titanate. These may be used alone or as a mixture.

The addition polymerization of the lactone monomer, which is one step of the above production method, will be described in more detail. Regarding the mixing ratio of the polymer (A) having a hydroxyl group and the lactone monomer, the ratio of the former (A) in the total 100 parts by weight of both is 0.1 to 30% by weight, preferably 1 to
15% by weight, more preferably 2 to 10% by weight. When the ratio is less than 0.1 parts by weight, the amount of hydroxyl groups is small, and eventually the amount of carboxyl groups produced by the reaction with an acid anhydride is small, and the high acid value lactone polymer (C) of the present invention is used on the market. 30% by weight
If it exceeds the range, the property as a lactone polymer, particularly the flexibility is lost, and the advantage of being used as a pressure-sensitive adhesive, an adhesive, a paint, a polymer plasticizer, etc. is lost, which is not preferable.

The addition amount of the polymerization catalyst is 100 in total for both raw materials.
The amount is 0.001 to 0.1 part by weight, preferably 0.002 to 0.05 part by weight, and more preferably 0.005 to 0.01 part by weight. When the amount of the catalyst is 0.
When the amount is less than 001 parts by weight, the polymerization rate of the lactone monomer is slow, while when the amount is more than 0.1 parts by weight, the obtained lactone polymer is colored or the thermal stability is deteriorated. It is not preferable because it may occur.

The polymerization temperature is 50 to 250 ° C., preferably 100 to 220 ° C., more preferably 16.
It is in the range of 0 to 200 ° C. If the temperature is below 50 ° C,
When the polymerization rate of the lactone monomer is slow and, conversely, it exceeds 250 ° C., a thermal decomposition reaction of the lactone polymer occurs, which causes coloration or a decomposed product, which is not preferable.

The typical high-hydroxyl lactone polymer (B) thus obtained is represented by the following general formula (3).

[Chemical 9]

The reaction between the terminal hydroxyl group of the high hydroxyl group lactone polymer (B) produced in the above process and the acid anhydride will be described in more detail. As the acid anhydride in the production method of the present invention, any acid anhydride can be used without particular limitation, but particularly succinic anhydride, phthalic anhydride, maleic anhydride, benzenetricarboxylic acid anhydride,
Benzenetetracarboxylic acid monoanhydride, benzenetetracarboxylic dianhydride, tetrahydrophthalic anhydride and hexahydrophthalic anhydride are preferred.

The reaction temperature between the terminal hydroxyl group of the high hydroxyl value lactone polymer (B) and the acid anhydride is in the range of 40 to 240 ° C., and it can be easily carried out by mixing both. 40
If the temperature is lower than 0 ° C, the reaction rate is slow, and if the temperature is higher than 240 ° C, gelation may occur due to a crosslinking reaction or the like, which is not preferable. The reaction temperature is preferably 60 to 160 ° C., more preferably 80 to 120 ° C., and the high acid value lactone polymer (C ₁ ) can be stably produced without coloring or high molecular weight.

The ratio of the number of moles of terminal hydroxyl groups of the high hydroxyl value lactone polymer (B) to the number of moles of acid anhydride is 1
It can be easily set by adjusting the charging amount to an arbitrary ratio in the range of 0: 1 to 1: 2. However, for the purpose of completely preventing the increase in the molecular weight, a ratio range of 1: 1 to 1: 1.2 in which the number of moles of the acid anhydride is slightly larger than the number of moles of the terminal hydroxyl group is the most easy to produce and is preferable.

The high acid number lactone polymer (C ₂ ) can be produced by a method of addition-polymerizing a lactone monomer using a polymer having 10 to 1,000 carboxyl groups in the molecule as an initiator. . 1 in the molecule used in the method for producing the high acid value lactone polymer (C ₂ ) of the present invention
Examples of the polymer having 0 to 1,000 carboxyl groups include oligomers, polymers and other radical polymerizations of compounds having both a radical polymerizable double bond and a carboxyl group in the molecule such as (meth) acrylic acid. Examples thereof include copolymers with a polymerizable monomer and graft modified products with various polymers. Generally, oligomers and polymers of (meth) acrylic acid, (meth) acrylic acid and styrene and / or (meth) acrylic acid. A copolymer with an ester is preferably used.

The typical polymer having a carboxyl group is represented by the following general formula (4).

[0033]

[Chemical 10]

Examples of the lactone monomer include methylated caprolactone such as ε-caprolactone and 4-methylcaprolactone, δ-valerolactone, β-propiolactone, and a mixture of two or more thereof, among which industrial The most beneficial ε-caprolactone is preferably used.

The acid catalyst used in the present production method may be either an inorganic acid or an organic acid, and specific examples thereof include sulfuric acid, hydrochloric acid, phosphoric acid, paratoluenesulfonic acid (hereinafter referred to as PTS), methane. Examples thereof include sulfonic acid and trifluoroacetic acid.

In the present production method, the mixing ratio of the polymer having a carboxyl group and the lactone monomer is
Of the total 100% by weight of both, the former accounts for 0.1 to 30% by weight, preferably 1 to 15% by weight, and more preferably 2 to 10% by weight. When the above ratio is less than 0.1% by weight, the amount of carboxyl group is small, and it cannot be used for the market application of the high acid value lactone polymer (C) of the present invention. On the contrary, when it exceeds 30% by weight, it becomes a lactone polymer. Is not preferable because it loses its property, especially flexibility and loses the merits of being used for pressure-sensitive adhesives, adhesives, paints, polymer plasticizers, etc.

The acid catalyst is added in an amount of 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of both raw materials. Is. When the amount of the catalyst is less than 0.01 part by weight, the polymerization rate of the lactone monomer is slow, and when it is more than 5 parts by weight, the obtained lactone polymer is colored or is thermally stable. It is not preferable because the property may be reduced.

The polymerization temperature is 50 to 250 ° C., preferably 100 to 220 ° C., more preferably 16.
It is in the range of 0 to 200 ° C. If the temperature is below 50 ° C,
When the polymerization rate of the lactone monomer is slow and, conversely, it exceeds 250 ° C., a thermal decomposition reaction of the lactone polymer occurs, which causes coloration or a decomposed product, which is not preferable.

As a reaction device in each of the above-mentioned methods for producing the high acid value lactone polymer (C ₁ ) or (C ₂ ) of the present invention, a known reaction device can be used without any problem. Specifically, a stirring blade type batch reactor, a semi-continuous and continuous reactor, a kneader mixer, a screw mixer such as an extruder, a static mixer reactor, and a reactor in which these are continuously connected And so on.

In each production method of the present invention, the order of addition of raw materials and catalysts and the method of addition are not limited at all, but the amount of water contained in the raw materials is 0.5% by weight or less, preferably 0.1% by weight. % Or less, more preferably 0.05% by weight or less. The amount of water contained in the raw material is 0.
If the amount exceeds 5% by weight, addition polymerization of the lactone monomer from water occurs to form a polylactone oligomer, which may cause a functional failure depending on the application, which is not preferable. Furthermore, in each of the production methods of the present invention, it is possible to carry out mixing of any diluent solvent and additives such as a stabilizer without any trouble.

[0041]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto.

(Production Example: Production of high hydroxyl value lactone polymer (B)) Polyvinyl alcohol (Kuraray Co., Ltd. "PVA-403",
Saponification degree 81.5 ± 1.5, degree of polymerization 300) 100 g,
900 g of ε-caprolactone and 0.05 g of monobutyltin tris (2-ethylhexanate) as a polymerization catalyst
Was added, the temperature was raised to 160 ° C., and melt kneading was performed for 3 hours. The obtained high hydroxyl value lactone polymer was a white wax. Standard polystyrene equivalent number average molecular weight by GPC measurement of this product, number of theoretical hydroxyl groups per molecule,
Theoretical number of moles of hydroxyl group per 1 g of resin and JIS described below
The number of moles of hydroxyl groups measured by the titration method according to K-1577 is also shown in Table 1.

(Examples 1 to 3) In a 500 ml glass flask, 300 g of the high hydroxyl group lactone polymer (B) obtained in Production Example and the acid anhydrides shown in Table 1 were added.
The amount described in 1 was added, and the mixture was stirred at 120 ° C. for 1 hour. Standard polystyrene-equivalent number average molecular weight of the obtained high acid value lactone polymer by GPC measurement, number of theoretical hydroxyl groups per molecule, number of carboxyl groups, number of theoretical hydroxyl groups per 1 g of resin, number of carboxyl groups and JIS described later.
Table 1 shows the number of moles of hydroxyl group and the number of carboxyl group measured per 1 g of resin by the titration method according to K-1577.
It is also described in.

(Example 4) A polyvinyl alcohol ("PVA1" manufactured by Kuraray Co., Ltd.) was placed in a 1-liter glass flask.
17 ", saponification degree 98.0 ± 0.5, polymerization degree 1700)
80 g, ε-caprolactone 720 g and polymerization catalyst monobutyltin tris (2-ethylhexanate) 0.
05 g was added, the temperature was raised to 160 ° C., and melt kneading was performed for 3 hours. After cooling to 100 ° C., 115 g of maleic anhydride was dissolved in 100 ml of toluene and added dropwise. Further, the temperature was raised to 120 ° C. while deaerating toluene, and after the temperature was raised, the mixture was stirred for 30 minutes. With respect to the obtained high acid value lactone polymer, the same properties as in Example 1 were measured,
The results are shown in Table-1.

Example 5 In a 1-liter glass flask, 200 g of styrene-methacrylic acid copolymer ("Leurex A-14" manufactured by Dainippon Ink and Chemicals, Inc.) was added.
-800 g of caprolactone and 4 g of PTS as an acid catalyst were added, the temperature was raised to 160 ° C, and melt kneading was carried out for 6 hours. 100 g of the obtained high acid value lactone polymer was dissolved in 1 liter of ethyl acetate, and washed with neutral water three times using an extractor to remove PTS as an acid catalyst. From the obtained dope of ethyl acetate, using an evaporator and a vacuum pump,
93.7 g of a polymer from which ethyl acetate was removed was obtained. This product was measured for the same properties as in Example 1, and the results are shown in Table 1.

[0046]

[Table 1]

(Titration Method) Approximately 0.5 g of the sample to be measured (0.5 ± 0.05 g is precisely weighed to 0.1 mg) was weighed into a 200 ml Erlenmeyer flask with a ground stopper, and a solution of phthalic anhydride in pyridine was measured. Accurately add 25 ml (42 g phthalic anhydride / 300 ml pyridine) with a whole pipette. Attach an air condenser to this and heat for 1 hour in a constant temperature bath at 98 ± 2 ° C. with occasional gentle shaking. Then, it is taken out of the constant temperature bath and allowed to reach room temperature, and 10 ml of pyridine is used to wash off the air condenser and the deposits on the flask wall in an Erlenmeyer flask with a ground stopper. Accurately add 50 ml of 0.5 N sodium hydroxide standard solution whose titer was measured in advance with a whole pipette, titrate with 0.5 N sodium hydroxide standard solution using phenolphthalein as an indicator, and keep the red color for 30 seconds. Set as the end point. Perform an empty experiment under the same conditions. Further, approximately 1.0 g (1.0 ± 0.05 g) of an acetone solution of the measurement sample was titrated with the above 0.5 N sodium hydroxide standard solution, and the number of moles of carboxyl group per 1 g of resin (AV) was measured.
Also ask in advance. The number of moles of hydroxyl group per 1 g of resin is calculated by the following formula.

[0048]

[Equation 1]

[0049]

As described in detail above, according to the present invention, a multi-branched type adhesive, adhesive, cured material, polymer plasticizer, polyamide resin modifier, compatibilizer, paint, alkaline water dispersibility It has become possible to provide a high acid value lactone polymer that can be widely used for binders, inks, biodegradable applications and medical applications.

Claims (4)

(57) [Claims] 1. A polymer represented by the following general formula (1): 1 g
Number of moles of carboxyl group per unit is 1 × 10 ^{-4 to} 5 × 10 ^-2
mol, the number of carboxyl groups per molecule is 10 to 15,0
00 and number average molecular weight of 20,000 to 2,000
High acid number lactone polymer characterized by being in the range of 10,000. [Chemical 1] 2. A polymer represented by the following general formula (2): 1 g
Number of moles of carboxyl group per unit is 1 × 10 ^{-4 to} 5 × 10 ^-2
mol, the number of carboxyl groups per molecule is 10 to 15,0
00 and number average molecular weight of 20,000 to 2,000
High acid number lactone polymer characterized by being in the range of 10,000. [Chemical 2] 3. A method of reacting all or part of the hydroxyl groups of a high hydroxyl value lactone polymer represented by the following general formula (3) having 10 to 5,000 hydroxyl groups in the molecule with an acid anhydride. The method for producing a high acid value lactone polymer according to claim 1. [Chemical 3] 4. A polymer represented by the following general formula (4) having 10 to 1,000 carboxyl groups in the molecule, 0.1 to 30% by weight, and a lactone monomer 99.9 to.
The high acid value lactone polymer according to claim 2, wherein 0.01 to 5 parts by weight of an acid catalyst is melt-kneaded with 100 parts by weight of a mixture consisting of 70% by weight (the total of both is 100% by weight). Manufacturing method. [Chemical 4]