阅读说明：本技术 一种端羟基不饱和聚酰胺及其制备方法和应用 (Hydroxyl-terminated unsaturated polyamide and preparation method and application thereof ) 是由 曹玉阳 晋云全 纪学顺 孙常青 于 2020-06-20 设计创作，主要内容包括：本发明提供一种端羟基不饱和聚酰胺,采用包括如下组分的原料反应制得：a)至少一种官能度为2～3且数均分子量在60～1000克/摩尔的多元胺；b)至少一种官能度为2～3且数均分子量在60～500克/摩尔的多元酸；c)包含羟基的一元胺；d)至少一种包含至少一个能与羟基基团反应的反应性基团且数均分子量在60～500克/摩尔的烯属不饱和化合物。本发明的端羟基不饱和聚酰胺可以用于制备不饱和聚氨酯分散体,其制备的木器漆具有成膜温度低、强度高、耐性高等优点。(The invention provides hydroxyl-terminated unsaturated polyamide which is prepared by adopting the reaction of the following raw materials: a) at least one polyamine having a functionality of 2 to 3 and a number average molecular weight of 60 to 1000 g/mol; b) at least one polyacid having a functionality of 2 to 3 and a number average molecular weight of 60 to 500 g/mol; c) a monoamine comprising a hydroxyl group; d) at least one ethylenically unsaturated compound comprising at least one reactive group capable of reacting with hydroxyl groups and having a number average molecular weight of 60 to 500 g/mol. The hydroxyl-terminated unsaturated polyamide can be used for preparing unsaturated polyurethane dispersoid, and the prepared wood lacquer has the advantages of low film-forming temperature, high strength, high resistance and the like.)

1. The hydroxyl-terminated unsaturated polyamide is characterized by being prepared by reacting the following raw materials:

a) at least one polyamine having a functionality of 2 to 3 and a number average molecular weight of 60 to 1000 g/mol;

b) at least one polyacid having a functionality of 2 to 3 and a number average molecular weight of 60 to 500 g/mol;

c) a monoamine comprising a hydroxyl group;

d) at least one ethylenically unsaturated compound comprising at least one reactive group capable of reacting with hydroxyl groups and having a number average molecular weight of 60 to 500 g/mol.

2. The hydroxyl-terminated unsaturated polyamide according to claim 1,

the component c) is a monoamine c1) containing one hydroxyl group and having a number average molecular weight of 60-400 g/mol and a monoamine c2) containing at least two hydroxyl groups and having a number average molecular weight of 60-400 g/mol, wherein the amino group is selected from primary amino groups or secondary amino groups, and the c2) accounts for 15-70% of the component c) in a molar ratio.

3. The hydroxyl-terminated unsaturated polyamide according to claim 2,

the molar ratio of the component b) to the component a) is 1.4 to 1.8; and/or the presence of a gas in the gas,

the molar ratio of component d) to component c2) is from 0.5 to 1.6.

4. The hydroxyl-terminated unsaturated polyamide according to claim 2 or 3,

based on 100 percent of the solid weight of the hydroxyl-terminated unsaturated polyamide,

the addition amount of the component a) is 25-65%, preferably 31-58 wt%; and/or the presence of a gas in the gas,

the addition amount of the component b) is 10-50%, preferably 25-40 wt%; and/or the presence of a gas in the gas,

the addition amount of the component c1) is 0.1-20%, preferably 1.2-10 wt%; and/or the presence of a gas in the gas,

the addition amount of the component c2) is 1-25%, preferably 3.6-16.5 wt%; and/or the presence of a gas in the gas,

the amount of the component d) added is 1-25%, preferably 6-18 wt%.

5. The hydroxyl-terminated unsaturated polyamide according to any one of claims 1 to 4,

the polyamine described in component a) is selected from one or more of 1, 2-diamino-2-methylpropane, 1, 7-heptanediamine, 1, 8-octanediamine, xylylenediamine, 2, 5-dimethyl-2, 5-hexanediamine, 1, 9-nonanediamine, dimethylpropylenediamine, 2-methyl-1, 5-pentanediamine, ethylenediamine, hexamethylenediamine, piperazine, pentamethylenediamine, polyetheramine (molecular weight 200-; and/or

The polybasic acid of component b) is selected from one or more of oxalic acid, glutaric acid, malonic acid, adipic acid, succinic acid, suberic acid, sebacic acid, azelaic acid, dodecanedioic acid, pimelic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid and 1, 4 and 1, 3-cyclohexanedicarboxylic acids, preferably adipic acid.

6. The hydroxyl-terminated unsaturated polyamide according to any one of claims 2 to 5, characterized in that component c1) is selected from the group consisting of ethanolamine, o-hydroxyaniline; (c2) selected from diethanolamine.

7. The hydroxyl-terminated unsaturated polyamide according to any one of claims 1 to 6, characterized in that component d) is isocyanatoethyl acrylate and/or isocyanatoethyl methacrylate.

8. A process for the preparation of a hydroxyl-terminated unsaturated polyamide according to any one of claims 1 to 7, characterized in that it comprises the following steps:

(1) loading a) and b) into a reactor under nitrogen atmosphere for reaction until the amine value is reduced to be below 0.1 mg/g;

(2) adding the component c2) into the reactor in the step (1), continuously adding the component c1) after reacting for 1-2 h, and then continuously reacting the mixture until the amine value is reduced to be below 0.1 mg/g;

(3) dehydrating the polymer obtained in the step (2), preferably heating to 120-170 ℃, and introducing vacuum for dehydration for 30 min-2 h;

(4) and (4) adding the component d) into the polymer obtained after dehydration in the step (3) until the NCO% in the system is below 0.1 wt%, and finishing the reaction to obtain the hydroxyl-terminated unsaturated polyamide.

9. The process for producing a hydroxyl-terminated unsaturated polyamide according to claim 6,

in the steps (1) and (2), the reaction temperature is 170-240 ℃; and/or the presence of a gas in the gas,

in the step (4), the reaction temperature is 70-110 ℃.

10. Use of a hydroxyl-terminated unsaturated polyamide according to any one of claims 1 to 7 or prepared by a method according to any one of claims 8 to 9 for the preparation of an unsaturated polyurethane dispersion for use in the field of wood lacquers.

11. An unsaturated polyurethane dispersion prepared from raw materials comprising:

based on 100% of the weight of the solid parts of the unsaturated polyurethane dispersion,

Technical Field

The invention belongs to the field of polymer chemistry, and particularly relates to unsaturated polyamide containing terminal hydroxyl, a preparation method and application thereof.

Background

Compared with polyester, polyamide has better hydrolysis resistance, and compared with polyether, polyamide has better strength, heat resistance, solvent resistance and UV radiation resistance. However, the polyamide has a high molecular weight and a high glass transition temperature, so that the polyamide is difficult to apply to the field of waterborne polyurethane. The preparation of comb-type polyamide prepolymer for UV curing plastic coating published in 2004 'coating industry', Zuojinfeng et al, describes that a low relative molecular mass polyamide resin and ethyl acrylate carbamate-based monoisocyanate are subjected to addition reaction to prepare a comb-type prepolymer which takes polyamide as a main chain and ethyl acrylate dicarbamate as a side chain, and the comb-type prepolymer can be used for UV curing coating, but the end group of the comb-type prepolymer is an acrylate bond, and cannot be applied to a waterborne polyurethane photocuring system through reaction.

Chinese published patent CN105121491A discloses an amine-terminated polyamide oligomer that can be used in water-based polyamide-urea dispersions, but because of its lack of unsaturated double bonds, its application in the field of photocuring results in low crosslinking density and relatively poor properties of chemical resistance, hardness, scratch resistance, etc.

Therefore, it is required to develop a polyamide product with unsaturated double bonds, which can be used for water-based unsaturated polyurethane, and can be applied to the field of wood lacquer to provide better properties of hydrolysis resistance, solvent resistance and the like.

Disclosure of Invention

The invention aims to provide hydroxyl-terminated unsaturated polyamide and a preparation method thereof, and the obtained unsaturated polyamide has better hydrolysis resistance and higher initiation activity and contains hydroxyl capable of reacting with NCO, so that the hydroxyl-terminated unsaturated polyamide can be applied to preparation of unsaturated polyurethane dispersoid.

The invention also aims to provide the application of the hydroxyl-terminated unsaturated polyamide in preparing the unsaturated polyurethane dispersoid, and the obtained unsaturated polyurethane dispersoid is used in the field of wood lacquer, so that the wood lacquer has the characteristics of hydrolysis resistance, high strength and good solvent resistance.

In order to achieve the above purpose, the technical scheme of the invention is as follows:

in a first aspect, the present invention provides a hydroxyl-terminated unsaturated polyamide prepared by reacting raw materials comprising:

a) at least one polyamine having a functionality of 2 to 3 and a number average molecular weight of 60 to 1000 g/mol;

b) at least one polyacid having a functionality of 2 to 3 and a number average molecular weight of 60 to 500 g/mol;

c) a monoamine comprising a hydroxyl group;

d) at least one ethylenically unsaturated compound comprising at least one reactive group capable of reacting with hydroxyl groups and having a number average molecular weight of 60 to 500 g/mol.

Preferably, in the present invention, the molar ratio of the component b) to the component a) is 1.4 to 1.8. If the molar ratio of the component b) to the component a) exceeds 1.8, the molecular weight of the obtained unsaturated polyamide is low, and the emulsion obtained by applying the unsaturated polyamide to aqueous UV has poor film forming performance and is easy to crack; if the molar ratio of the component b) to the component a) is less than 1.4, the molecular weight of the obtained unsaturated polyamide is high, so that the obtained unsaturated polyamide is not easy to dissolve in a good solvent of polyurethane in the process of aqueous UV prepolymerization and the performance of the obtained emulsion is poor.

Preferably, in the present invention, the component c) is a monoamine c1) containing one hydroxyl group and having a number average molecular weight of 60 to 400 g/mol and a monoamine c2) containing at least two hydroxyl groups and having a number average molecular weight of 60 to 400 g/mol, wherein the amino group is selected from primary or secondary amino groups, and preferably the c2) is present in a molar ratio of 15 to 70% based on the component c). More preferably, said c2) is present in a molar ratio of 25 to 55.5% with respect to component c). If the molar ratio of c2) to component c) exceeds 70%, the unsaturated polyamide will have too many hydroxyl groups, resulting in too many cross-links during the aqueous UV pre-polymerization, which will affect the dispersion of the final resin; if the molar ratio of c2) to component c) is less than 15%, the unsaturated polyamide will have too few hydroxyl groups, resulting in a lower molecular weight of the aqueous UV resin, which affects the properties of the final resin, such as hardness and strength.

Preferably, in the present invention, the molar ratio of the component d) to the component c2) is 0.5 to 1.6. More preferably, the molar ratio of component d) to component c2) is from 0.8 to 1.4. If the molar ratio of the component d) to the component c2) exceeds 1.6, the acrylic ester bonds in the unsaturated polyamide are excessive, so that the storage stability of the aqueous UV resin is reduced; if the molar ratio of the component d) to the component c2) is less than 0.5, the unsaturated polyamide has too few acrylate bonds, so that the strength, hardness and chemical resistance of the finally obtained waterborne UV resin are reduced.

Preferably, in the present invention, the hydroxyl-terminated unsaturated polyamide is a polyamide having a hydroxyl group at a content of 100% by weight in terms of solid content,

the addition amount of the component a) is 25-65%, preferably 31-58 wt%; and/or the presence of a gas in the gas,

the addition amount of the component b) is 10-50%, preferably 25-40 wt%; and/or the presence of a gas in the gas,

the addition amount of the component c1) is 0.1-20%, preferably 1.2-10 wt%; and/or the presence of a gas in the gas,

the addition amount of the component c2) is 1-25%, preferably 3.6-16.5 wt%; and/or the presence of a gas in the gas,

the amount of the component d) added is 1-25%, preferably 6-18 wt%.

Preferably, in the present invention, the polyamine described in component a) is selected from one or more of 1, 2-diamino-2-methylpropane, 1, 7-heptanediamine, 1, 8-octanediamine, xylylenediamine, 2, 5-dimethyl-2, 5-hexanediamine, 1, 9-nonanediamine, dimethylpropylenediamine, 2-methyl-1, 5-pentanediamine, ethylenediamine, hexamethylenediamine, piperazine, pentamethylenediamine, polyetheramine (molecular weight 200-. And/or

The polybasic acid of component b) is selected from one or more of oxalic acid, glutaric acid, malonic acid, adipic acid, succinic acid, suberic acid, sebacic acid, azelaic acid, dodecanedioic acid, pimelic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid and 1, 4 or 1, 3-cyclohexanedicarboxylic acid, preferably adipic acid.

Preferably, component c1) is selected from ethanolamine, o-hydroxyaniline; (c2) selected from diethanolamine.

Preferably, component d) is isocyanatoethyl acrylate and/or isocyanatoethyl methacrylate. The addition of the component d) can provide high-activity unsaturated double bonds in the prepared polyamide, and the application of the component d) in the preparation of unsaturated polyurethane dispersions can improve the curing speed, curing efficiency, hardness and chemical resistance of the resin and the like.

In a second aspect, the present invention provides a method for preparing the above hydroxyl-terminated unsaturated polyamide, comprising the steps of:

(1) loading a) and b) into a reactor under nitrogen atmosphere, and heating the reactor until the amine value is reduced to below 0.1 mg/g;

(2) dropwise adding the component c2) into the reactor in the step (1), continuously dropwise adding the component c1) after reacting for 1-2 h, and then continuously reacting the mixture until the amine value is reduced to be below 0.1 mg/g;

(3) dehydrating the polymer obtained in the step (2), preferably heating to 120-170 ℃, and introducing vacuum for dehydration for 30 min-2 h;

(4) and (4) adding the component d) into the polymer obtained in the step (3) until the NCO% in the system is below 0.1 wt%, and finishing the reaction to obtain the hydroxyl-terminated unsaturated polyamide.

In the steps (1) and (2), the reaction temperature is 170-240 ℃; and/or the presence of a gas in the gas,

in the step (4), the reaction temperature is 70-110 ℃;

in a third aspect, the present invention also provides a scheme in which the above-mentioned hydroxyl-terminated unsaturated polyamide or the hydroxyl-terminated unsaturated polyamide produced by the above-mentioned production method can be used for producing an unsaturated polyurethane dispersion.

In a fourth aspect, the present invention also provides an unsaturated polyurethane dispersion comprising the above hydroxyl-terminated unsaturated polyamide or the hydroxyl-terminated unsaturated polyamide produced by the above production method.

As a preferred embodiment, an unsaturated polyurethane dispersion is prepared from the following raw materials:

based on 100% of the weight of the solid parts of the unsaturated polyurethane dispersion,

the invention also provides a process for preparing an unsaturated polyurethane dispersion:

(1) putting 4, 4-dicyclohexylmethane diisocyanate, dehydrated hydroxyl-terminated unsaturated polyamide, poly (neopentyl glycol adipate) diol, polyethylene glycol monomethyl ether, neopentyl glycol, trimethylolpropane, 2-dimethylolpropionic acid and a solvent into a reaction container under the protection of inert gas for reaction until the NCO content reaches a theoretical value to obtain a prepolymer of the terminal isocyanate;

(2) cooling the isocyanate-terminated prepolymer, adding a solvent for dilution, continuously cooling and stirring, adding triethylamine with a selected weight for neutralization, stirring for reaction, adding dipentaerythritol hexaacrylate with a selected weight after neutralization is finished, and after stirring uniformly, adding water for dispersion under rapid stirring to obtain an emulsion;

(3) and adding ethylene diamine aqueous solution with the selected weight into the emulsion to carry out chain extension reaction to obtain the unsaturated polyurethane dispersion.

Wherein the rapid stirring is stirring at the rotating speed of 800-2500.

The inert atmosphere is preferably nitrogen.

Preferably, in the above-mentioned process for producing a polyurethane polyurea aqueous dispersion of the present invention,

in the aqueous solution of ethylenediamine, the weight of water is 2 to 8 times of the weight of ethylenediamine, and preferably, the weight of water is 4 to 6 times of the weight of ethylenediamine.

Preferably, in the above-mentioned process for producing a polyurethane polyurea aqueous dispersion of the present invention,

in the step (1), the reaction temperature is 70-90 ℃. And/or the presence of a gas in the gas,

in the step (2), the isocyanate-terminated prepolymer is cooled to 30-55 ℃, a solvent is added for dilution, the temperature is continuously cooled to 10-40 ℃, and triethylamine with the selected weight is added for neutralization under the stirring condition. And/or the presence of a gas in the gas,

in the step (3), adding an ethylene diamine aqueous solution into the emulsion, carrying out chain extension at 20-60 ℃, and reacting for more than 2 min.

Preferably, in the above-mentioned process for producing a polyurethane polyurea aqueous dispersion of the present invention,

in the step (1) and the step (2), the solvent is selected from at least one of acetone, methyl ethyl ketone, tert-butyl methyl ether and tetrahydrofuran, preferably selected from methyl ethyl ketone or acetone, and more preferably selected from acetone.

In the step (2), water is added under stirring for dispersing for 1-18 minutes, and preferably, water is added under stirring for dispersing for 5-15 minutes. And/or the presence of a gas in the gas,

after the step (3), the method further comprises the following steps: the solvent is partially or completely removed.

According to the invention, polyamide is modified, and the structure of the polyamide is controlled, so that the polyamide can be grafted into a polyurethane chain segment through hydroxyl. And unsaturated double bonds are introduced into chain segments through reaction, so that the obtained polyamide is introduced with unsaturated groups into soft segments, can be applied to the field of radiation photocuring, provides coatings for different substrates such as wood, plastic and metal, and has the advantages of higher storage stability, better hardness, chemical resistance and scratch resistance and lower minimum film-forming temperature.

Detailed Description

In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.

The following examples and comparative examples have the following raw materials and sources:

adipic acid: functionality of 2 (peruvian constant liter);

d230: polyetheramine, Mn 230, functionality 2 (basf);

d400: polyetheramine, Mn 400, functionality 2 (basf)

Ethanolamine: amino functionality of 1 (alatin);

diethanolamine: amino functionality of 1 (alatin);

isocyanate ethyl acrylate: isocyanate functionality of 1 (alpha chemical);

isocyanoethyl methacrylate: (ii) alatin;

polyester polyol I: poly neopentyl glycol adipate diol, Mn 1000, functionality 2(WHP-105, wanhua chemistry);

MPEG-1200: monofunctional polyether, polyethylene glycol monomethyl ether, the number average molecular weight is 1200, the number of ethylene oxide groups is 26 (Hunan petrochemical);

NPG: neopentyl glycol (basf);

TMP: trimethylolpropane (Wanhua chemical)

DMPA: 2, 2-dimethylolpropionic acid (Perstrop);

HMDI: 4, 4-dicyclohexylmethane diisocyanate (Vanhua Chemicals)

DPHA: dipentaerythritol hexaacrylate (Jiangsu Sanmu chemical industry)

The parameters in the following examples were determined as follows:

average particle size: diluting the aqueous unsaturated polyurethane dispersion with water to a concentration of 0.5 wt.%, as determined using Marvens Nano-ZS 90;

determination of the NCO: the content of-NCO in the polyurethane synthesis process is determined according to the chemical industry standard of the people's republic of China for determining the content of isocyanate groups in the polyurethane prepolymer HG/T2409-92.

And (3) determination of amine value: a0.1 mol/L milligram (mg/g) of potassium hydroxide equivalent to hydrochloric acid consumed by titrating 1g (to the nearest 0.0001g) of amine in a sample using an automatic titrator model ZDJ-5B.