WO2020138660A1 - Chain extender composition for polyurethane - Google Patents

Abstract

The present invention relates to a chain extender composition for polyurethane. The chain extender composition for polyurethane, according to the present invention, contains 0.5 to 10 parts by weight of one or more ingredients selected from among a catalyst for controlling hardness and a catalyst for controlling a curing rate per 100 parts by weight of one or more ingredients selected from among aldimine, ketamine, and a polyaspartic ester.

Description

Chain extender composition for polyurethane

The present invention relates to a chain extender composition for polyurethane, and more specifically, it is possible to replace mocha (MOCA), which is an existing chain extender composition harmful to the human body used in the manufacture of polyurethane used as a raw material for waterproof floor coatings, etc. , It relates to an economical chain extender composition for polyurethane to impart an appropriate curing rate so as to have excellent hardness and workability.

In the production of polyurethane or polyurea, chain extenders or epoxy curing agents are used. MOCA (4,4'-Methylene bis (ortho-chloroaniline)) has been mainly used as the chain extender or epoxy curing agent. MOCA has been used for a long time as a chain extender that enables stable coating work by securing a suitable coating time after mixing the curing agent with improving the hardness of the waterproof and moisture-proof urethane paint, but is known to be harmful to the human body. According to the International Agency for Research on Cancer (IARC), MOCA is known to cause cancer in humans, and it has been confirmed that it causes tumors in many parts of experimental mice and rabbits and bladder tumors in dogs. (See Carcinogenicity of Some Aromatic Amines, Organic Dyes, and Related Exposures, The Lancet Oncology, Volume 9, Issue 4, Pages 322-323, April 2008).

In addition, MOCA has been designated as a substance to be prohibited from being manufactured, imported and sold for products containing 0.1% or more since September 2020, and thus, a chain extender composition to replace it is urgently required.

In order to solve this problem, Patent No. 10-1777432 "Paint composition" tried to solve by mixing a plurality of primary and secondary bis-aromatic diamines, but the diamine used was expensive, so the replacement effect of MOCA was expected. It is not going crazy.

For a similar reason, a number of MOCA alternative development products currently exist, but there is a need to develop a chain extender composition for polyurethane that is economical and impaired to the human body because it is expensive and difficult to secure an appropriate curing time.

Therefore, the problem to be solved by the present invention is to solve the above problems, and it is economical because it is an inexpensive alternative to the existing chain extender composition MOCA, which is harmful to the human body as a carcinogen, and has a suitable curing speed and is suitable for securing curing time. It is yet another object to provide a chain extender composition for polyurethane used as a raw material, such as a waterproof flooring coating that has been impaired on the human body.

The chain extender composition for polyurethane according to the present invention for solving the above problems is at least one component selected from the catalyst for controlling hardness and a catalyst for controlling curing speed per 100 parts by weight of at least one component selected from aldimine, ketamine and polyaspartic ester. 0.5 to 10 parts by weight.

The adimine is prepared by reaction of aldehyde and amine, the ketamine is prepared by reaction of ketone and amine, and the polyaspartic ester can be prepared by reaction of alkenyl ester and amine.

The aldehyde may be one or two or more mixtures selected from formaldehyde, acetaldehyde, paraformaldehyde, propionaldehyde, benzaldehyde, butylaldehyde, isobutylaldehyde and 2-ethylhexanal.

The ketone may be one or two or more mixtures selected from acetone, methyl ethyl ketone, methyl butyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone and acetophenone.

The alkenyl ester may be a mixture of one or two phases selected from dialkyl maleates and dialkyl fumarates.

The amine is isophorone diamine, polyoxypropylene diamine, polyoxypropylene triamine, methanediamine, 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,3-diaminopentane , 1,5-diaminomethylpentane, 1,3- and 1,4-xylenediamine, 1,6-hexamethylenediamine, phenylenediamine, tolylenediamine, bis(4-aminophenyl)methane, bis(4 -Aminocyclohexyl)methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, 2,4- and 2,6-diethyltoluenediamine (DETDA), 2,4- and 2, 6-dimethyl toluenediamine.

The catalyst for controlling the curing rate is an organic acid such as benzoic acid or oxalic acid, an aromatic chloride which is benzene chloride or benzyl chloride (Bz-Cl), an inorganic acid selected from hydrochloric acid or sulfuric acid and phosphoric acid, and a chloride and chlorine oxide containing sulfur or phosphorus It may be a mixture of one or two or more.

The hardness control catalyst is isophorone diamine, methanediamine, 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,3-diaminopentane, 1,5-diaminomethylpentane , 1,3- and 1,4-xylenediamine, 1,6-hexamethylenediamine, phenylenediamine, tolylenediamine, bis(4-aminophenyl)methane, bis(4-aminocyclohexyl)methane, 1, 2-, 1,3- and 1,4-diaminocyclohexane, 2,4- and 2,6-diethyltoluenediamine (DETDA), 2,4- and 2,6-dimethyltoluenediamine (DMTDA), Phenylcarmine, Melamine, Huntsman's Jeffamine D-230, Jeffamine D-2000, Jeffamine D-5000 and Jeffamine T-403.

As described above, according to the polyurethane chain extender composition according to the present invention, it is a carcinogen and is a substitute for moca (MOCA), an existing chain extender composition harmful to the human body. It is suitable and economical, but it has the advantageous effect of being able to mass-produce polyurethane products, such as for waterproof floor coatings, at a low price by inhibiting the human body.

Specific details of other embodiments are included in the detailed description.

Advantages and features of the present invention, and methods for achieving them will be clarified with reference to embodiments described below in detail. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various different forms, and only the present embodiments make the disclosure of the present invention complete, and have ordinary knowledge in the technical field to which the present invention pertains. It is provided to fully inform the person of the scope of the invention, and the invention is only defined by the scope of the claims.

Hereinafter, a chain extender composition for polyurethane according to an embodiment of the present invention will be described in detail.

The chain extender composition for polyurethane according to an embodiment of the present invention is a catalyst for controlling hardness per 100 parts by weight of one or more components selected from pigments Aldimine, Ketimine and Polyaspartic ester (PAE) And 0.5 to 10 parts by weight of at least one component selected from the catalyst for controlling the curing rate.

The aldimine used in the present invention is synthesized by the reaction of aldehyde (Aldehyde) and amine (Amine), it is as shown in [Formula 1].

[Formula 1]

Here, R1 and R2 are aliphatic, alicyclic, and aromatic hydrocarbons and may be the same or different.

The skeleton of the diamine in which the amine is bonded to both sides can be an aliphatic, cycloaliphatic or aromatic hydrocarbon in any structure.

Aldimine synthesis from the reaction of the aldehyde (Aldehyde) and amine (Amine) is US Patent Registration Document US 5,856,420 (Jan.5,1999) "Bis (isobutyraldimine) of 1,4-diaminobutane in HDI trimer and biuret-based coatings Applicable as known from ", one or two or more selected from formaldehyde, acetaldehyde, paraformaldehyde, propionaldehyde, benzaldehyde, butylaldehyde, isobutylaldehyde (IBA) and 2-ethylhexanaldehyde as representative aldehydes that can be used. Mixtures are preferred. The aforementioned aldehydes represented by isobutyl aldehyde tend to react with amines and be easily converted to aldimine.

In addition, the amines are representative diamines that can be used, such as isophorone diamine (IPDA), polyoxypropylene diamine, polyoxypropylene triamine, methanediamine, 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylene Diamine, 1,3-diaminopentane, 1,5-diaminomethylpentane, 1,3- and 1,4-xylenediamine, 1,6-hexamethylenediamine, phenylenediamine, tolylenediamine, bis(4 -Aminophenyl)methane, bis(4-aminocyclohexyl)methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, 2,4- and 2,6-diethyltoluenediamine (DETDA ), 2,4- and 2,6-dimethyltoluenediamine (DMTDA). The aforementioned diamine represented by DETDA tends to be easily converted to aldimine by reaction with aldehyde, ketamine by reaction with ketone, and polyaspartic ester by reaction with alkenyl ester. The same applies to Formulas 2 and 3 below.

Representative synthetic examples: diethyltoluenediamine (DETDA) + isobutylaldehyde (IBA))

The actual synthesis of aldimine related to Example 1 of the present invention is DETDA 252 g (1.41 mol) and toluene in a three-necked flask equipped with a thermometer, nitrogen injection tube, cooling tube, and Dean Stark column, which is an experimental device. After adding 250 g, 225 g (3.12 mol) of isobutyl aldehyde was added dropwise while maintaining a temperature of 30° C. or less under nitrogen flow, and aged at 70° C. for 1.5 hours, and then the water produced during the reaction was decompressed with toluene at a temperature of 70° C. or less. Through the azeotropic distillation removal process, 367.5 g of adimine was obtained (yield 91.0%).

The ketamine is synthesized by the reaction of ketone and amine, as shown in [Formula 2] below.

[Formula 2]

Here, R1, R2, R3, and R4 are aliphatic, alicyclic, and aromatic hydrocarbons, which are the same or different. The skeleton of diamine can be an aliphatic, cycloaliphatic or aromatic hydrocarbon in any structure.

The synthesis of ketamine from the reaction of ketone and amine is applicable and known as available in US Patent Application Publication US 3,291,775 (November. 13, 1966) "Process for curing polyepoxides with a polyimine" The ketone may be one or more mixtures selected from acetone, methyl ethyl ketone (MEK), methyl butyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone and acetophenone. The aforementioned ketones represented by MEK tend to react with amines to be easily converted to ketamine.

Synthetic representative example: diethyltoluenediamine (DETDA) + methyl ethyl ketone (MEK)

The actual synthesis of ketamine related to the following Example 2 of the present invention was performed by adding DETDA 252 g (1.41 mol) and toluene 250 g into a three-necked flask equipped with a thermometer, a nitrogen injection tube, a cooling tube, and a Dean Stark column. 187 g (3.12 mol) of methyl ethyl ketone is added dropwise while maintaining a temperature below ℃, aged at 70° C. for 1.5 hours, and then 315 g through a reduced pressure azeotropic distillation process using toluene to generate moisture during the reaction at a temperature below 70° C. Ketamine was obtained (yield 85.0%).

The polyaspartic ester (Polyaspartic ester, PAE) is synthesized by the reaction of an alkenyl ester (Alkenyl ester) and an amine, as shown in [Formula 3].

[Formula 3]

Here, the skeleton of the diamine may be an aliphatic, cycloaliphatic or aromatic hydrocarbon in an arbitrary structure.

Synthesis of polyaspartic esters by reaction of the alkenyl ester and diamine is US Pat. No. 5,126,170 (Jan. 30, 1992) "Process for the production of polyurethane coatings" As known from the above, it is applicable, and the alkenyl esters that can be used include dialkyl maleates (where alkyl includes a range of 1 to 6 carbon atoms and typically corresponds to diethyl maleates) and dialkyl fumarates (where alkyl is It is preferred to be a mixture of one or two or more selected from among the range of 1 to 6 carbon atoms. The alkenyl ester represented by diethyl maleate (DEM) tends to be easily converted into an aspartic ester by reacting diamine and Michael addition to a double bond in the molecule.

Synthetic representative example: diethyl maleate (DEM) + isophorone diamine (IPDA)

The actual synthesis of polyaspartic ester (PAE) related to Example 3 below of the present invention is performed by adding 170 g (0.998 mol) of isophorone diamine (IPDA) to a three-necked flask equipped with a thermometer, a nitrogen injection tube, and a cooling tube. 510 g (yield 98.0%) of polyaspartic ester was obtained through a process of keeping 350 g (2.033 mol) of diethyl maleate dropwise for 12 hours while heating and maintaining the temperature below 30° C. under air flow.

On the other hand, as an application additive, there is a catalyst for controlling the curing rate and a catalyst for controlling the hardness for improving hardness.

The catalyst for controlling the curing rate is an organic acid such as benzoic acid or oxalic acid, an aromatic chloride which is benzene chloride or benzyl chloride (Bz-Cl), an inorganic acid selected from hydrochloric acid or sulfuric acid and phosphoric acid, and a chloride and chlorine oxide containing sulfur or phosphorus It may be a mixture of one or two or more. The catalyst for controlling the acid cure rate represented by benzyl chloride (Bz-Cl) generally exhibits an effect of retarding the reaction rate.

The hardness control catalyst is isophorone diamine, methanediamine, 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,3-diaminopentane, 1,5-diaminomethylpentane , 1,3- and 1,4-xylenediamine, 1,6-hexamethylenediamine, phenylenediamine, tolylenediamine, bis(4-aminophenyl)methane, bis(4-aminocyclohexyl)methane, 1, 2-, 1,3- and 1,4-diaminocyclohexane, 2,4- and 2,6-diethyltoluenediamine (DETDA), 2,4- and 2,6-dimethyltoluenediamine (DMTDA), Phenylcarmine, Melamine, Huntsman's Jeffamine D-230, Jeffamine D-2000, Jeffamine D-5000 and Jeffamine T-403. The aforementioned diamines represented by 2,4- and 2,6-diethyltoluenediamine (DETDA) react with urethane isocyanate, which increases the hardness, but the degree of hardness increase is somewhat dependent on the degree of steric hindrance of diamines. There may be differences.

Hereinafter, various practical examples and properties of the chain extender composition for polyurethane according to the present invention will be described in comparison with comparative examples.

Prior to the description, the chain extender composition for polyurethane according to the present invention and mocha (MOCA) are one component of the polyurethane used for waterproof floor coatings, etc., so the poly prepared using the polyurethane chain extender composition according to the present invention Various embodiments and properties of the urethane waterproof flooring material coating will be described in comparison with a comparative example of a polyurethane waterproof flooring material coating produced using MOCA.

The actual experimental method for comparing the examples and the comparative example is as follows.

70 parts by weight of plasticizer per 100 parts by weight of pigment, 45 parts by weight of polypropylene glycol having a number average molecular weight of 3000, 5 parts by weight of curing accelerator, main part having 5 parts by weight of at least one additive selected from dispersants and anti-settling agents and antifoaming agents, 5 parts by weight of propanediol having a number average molecular weight of 2000 per 100 parts by weight of polypropylene glycol having a number average molecular weight of 3000, 40 parts by weight of polypropylene glycol having a number average molecular weight of 1000, and 40 parts by weight of toluenediisocyanate 80 A curing agent having 70 parts by weight per 100 parts by weight of the main part, and a catalyst for controlling hardness per 100 parts by weight of one or more components selected from aldimine, ketimine, and polyaspartic ester, or partially polymerized for 2 to 3 hours at 85°C or It contains 0.5 to 10 parts by weight of one or more components of the catalyst for controlling the curing rate, and after mixing the polyurethane waterproof flooring coating material mixed with the chain extender having 1 to 5 parts by weight per 100 parts by weight of the main part, the viscosity reaches 100,000 cPs. An experimental method was selected to measure the cure rate in time and measure the hardness after 1 and 3 days with a Shore A hardness tester.

(Example 1)

Hardness as a catalyst to 1.663 wt g (1.16 amine equivalents (%) (amine molar equivalents 143.3)) of aldimine synthesized from diethyltoluenediamine (DETDA) and isobutylaldehyde as a chain extender at 100 wt g of main part and 70 wt g of curing agent The physical properties of the polyurethane polymer synthesized using 0.0050 to 0.0915 weight g of DETDA for control and 0.0050 to 0.0915 weight g of benzyl chloride (Bz-Cl) for adjusting the curing rate, alone or in combination, are shown in [Table 1].

On the other hand, after the reaction between the main part and the curing agent, unreacted residual isocyanate and the amine of the chain extender are combined to form a coating material of polyurethane or polyurea resin, so for comparison of the performance of the chain extender composition between Example 1 and Comparative Example, Since the equivalent (%) must be the same, in the case of the comparative example MOCA, when the amine equivalent (%) is equal to 1.16, it is 1.55 weight g in terms of weight.

The amine molar equivalent is the molecular weight corresponding to one amine group of the compound, the molecular weight of the aldimine mentioned in Example 1 is 286.6, and the number of amine groups in the molecule is two, so the amine molar equivalent of this aldimine is 143.3, and in the case of MOCA for comparison The molecular weight is 267.2 and the number of amine groups in the molecule is two, so the molar molar equivalent of MOCA is 133.6.

division			Comparative example	Example 1-1	Example 1-2	Example 1-3	Example 1-4
Main part (weight g)			100
Curing agent (weight g) (*1)			70
Chain extender	MOCA (weight g)		1.55
	MOCA amine equivalent (%)(*2)		1.16
	Aldimine (weight g)			1.663
	Aldimine amine equivalent (%) (*3)			1.16
	catalyst	DETDA (weight g)		0.0832			0.0499
		Bz-Cl (weight g)		0.0832	0.0499	0.0083	0.0832
Curing speed (time to reach 100,000 cPs) (*4)			58'35"	54'45"	53'58"	53'08"	61'30"
Hardness after 1 day (Shore A)			50	52	53	55	45
Hardness after 3 days (Shore A)			71	74	76	78	71
division			Example 1-5	Example 1-6	Example 1-7	Example 1-8	Example 1-9
Main part (weight g)			100
Curing agent (weight g) (*1)			70
Chain extender	MOCA (weight g)
	MOCA amine equivalent (%)(*2)
	Aldimine (weight g)		1.663
	Aldimine amine equivalent (%) (*3)		1.16
	catalyst	DETDA (weight g)	0.0499		0.0083
		Bz-Cl (weight g)	0.0499	0.0083	0.0832	0.0499	0.0083
Curing speed (time to reach 100,000 cPs) (*4)			60'10"	57'27"	62'12"	60'06"	58'20"
Hardness after 1 day (Shore A)			48	52	45	46	48
Hardness after 3 days (Shore A)			72	73	66	68	70
division			Example 1-10	Example 1-11	Example 1-12	Example 1-13	Example 1-14
Main part (weight g)			100
Curing agent (weight g) (*1)			70
Chain extender	MOCA (weight g)
	MOCA amine equivalent (%)(*2)
	Aldimine (weight g)		1.663
	Aldimine amine equivalent (%) (*3)		1.16
	catalyst	DETDA (weight g)	0.0083		0.0050		0.0915
		Bz-Cl (weight g)		0.0083		0.0050	0.0915
Curing speed (time to reach 100,000 cPs) (*4)			56'52"	60'35"	57'43"	63'03"	62'20"
Hardness after 1 day (Shore A)			47	45	40	38	63
Hardness after 3 days (Shore A)			68	64	60	58	85

<Physical property evaluation method>

(*1) The appropriate amount of the curing agent will vary depending on the properties of the polyurethane, but since the important aspect of Example 1 is a comparison of the performance of the chain extender, the amount of the curing agent is limited to 70 parts by weight and the physical properties according to the content of the chain extender. Comparative evaluation was conducted. (Hereinafter, the same to Examples 2 to 6)

(*2) MOCA amine equivalent (%) = used weight of MOCA used / MOCA amine molar equivalent (133.6) * 100

(*3) Aldimine amine equivalent (%) = used adimin used weight / Aldimine amine molar equivalent (143.3) * 100

(*4) The curing rate was measured at 25°C using a Brookfield LV type, Spindle 64, RPM 6 viscometer to measure the time to reach 100,000 cPs.

(*5) In order to compare the performances of MOCA and aldimine, the amine equivalents (%) of MOCA and aldimin were equally compared to 1.16.

<Results of physical property evaluation>

Similarity to the first embodiment to replace the conventional chain extender composition, MOCA, when the curing rate is too fast after mixing the subject and the curing agent, some curing occurs inside the mixed coating during the coating operation such as the actual waterproof floor coating. And the coating workability of the latter part is different, so that a stable painting operation cannot be achieved. On the contrary, if the curing speed is too slow, a problem may occur that the painting operation process time is delayed. In addition, if the hardness is too low, physical properties such as abrasion resistance are deteriorated, and the productability is reduced. If the hardness is too high, there is a problem that cracks or cracks may occur after construction.

When comparing the 14 compounding conditions of Examples 1-1 to 1-14 compared to Comparative Examples using MOCA as a conventional chain extender, the Examples 1-1 to Examples 1-11 are comparative examples in use. The curing rate of MOCA (53'08" to 62'12" when compared with 58'35" showed a curing rate similar to that of MOCA (within ±10%). In addition, the hardness after 1 day was 45 compared to the comparative example MOCA 50 It is similar to within 55 (within ±10%), and the hardness after 3 days is found to be similar with within 64 to 78 (within ±10%) compared to MOCA 71, so it has good curing speed and hardness, so when constructing waterproof floor coatings, etc. It was found that the workability can be secured, that is, in Example 1 of the present invention, despite the harmfulness, it is cured based on the deviation within about 10% compared to the currently used MOCA with proper work stability and good physical properties. Examples 1-1 to 1- comprising 0.5 to 10 parts by weight (0.0083 to 0.166 parts by weight) of one or more components of a catalyst for controlling hardness or a catalyst for controlling curing speed, per 100 parts by weight of adimine when converted to parts by weight having similar speed and hardness It was found that the chain extender composition of 11 can be used as a substitute for MOCA.

On the other hand, the hardness of Example 1-12 after 40 days is 40% lower than that of MOCA by using 0.005 wt g corresponding to 0.3 part by weight of DETDA less than 0.5 part by weight per 100 parts by weight of aldimine. The hardness after 3 days is 60, which is 15.5% lower than MOCA 71, and the hardness after 1 day in Example 1-13 using 0.005 wt g corresponding to 0.3 parts by weight of Bz-Cl is 38, which is 24% compared to MOCA 50 It was low, and the hardness after 3 days was 58, 18.3% lower than MOCA 71. In addition, the hardness after 1 day of Example 1-14, which is 0.183 weight g corresponding to 11 parts by weight of each of 5.5 parts by weight of DETDA and Bz-Cl, more than 10 parts by weight per 100 parts by weight of aldimine, is 26% compared to MOCA 50 It is high, and the hardness after 3 days is 85, which is 19.7% higher than MOCA 71, so it was confirmed that the physical property deviation was so large that it could not replace the performance of MOCA.

(Example 2)

Hardness as a catalyst to 1.66 wt g (1.16 amine equivalents (%) (amine molar equivalent 143.1)) of ketamine synthesized from diethyltoluenediamine (DETDA) and methyl ethyl ketone as a chain extender at 100 wt g of main part and 70 wt g of curing agent The properties of the polyurethane polymer synthesized using 0.0050 to 0.0913 weight g of DETDA for control and 0.0050 to 0.0913 weight of benzyl chloride (Bz-Cl) for adjusting the curing rate, alone or in combination, are shown in [Table 2].

Since the molecular weight of ketamine mentioned in Example 2 is 286.2 and the number of amine groups in the molecule is two, the amine molar equivalent of this ketimine is 143.1.

The evaluation method of physical properties is the same as in Example 1.

division			Comparative example	Example 2-1	Example 2-2	Example 2-3	Example 2-4
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)		1.55
	MOCA amine equivalent (%)		1.16
	Ketimine (weight g)			1.660
	Ketimine amine equivalent (%) (*1)			1.16
	catalyst	DETDA (weight g)		0.0830	0.0830	0.0830	0.0498
		Bz-Cl (weight g)		0.0830	0.0498	0.0083	0.0830
Curing speed (time to reach 100,000 cPs)			58'35"	54'31"	53'30"	52'38"	58'23"
Hardness after 1 day (Shore A)			50	53	54	55	48
Hardness after 3 days (Shore A)			71	75	76	77	72
division			Example 2-5	Example 2-6	Example 2-7	Example 2-8	Example 2-9
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)
	MOCA amine equivalent (%)
	Ketimine (weight g)		1.660
	Ketimine amine equivalent (%) (*1)		1.16
	catalyst	DETDA (weight g)	0.0498	0.0498	0.0083	0.0083	0.0083
		Bz-Cl (weight g)	0.0498	0.0083	0.0830	0.0498	0.0083
Curing speed (time to reach 100,000 cPs)			55'45"	54'55"	62'58"	60'10"	57'31"
Hardness after 1 day (Shore A)			51	53	44	46	48
Hardness after 3 days (Shore A)			73	75	66	68	70
division			Example 2-10	Example 2-11	Example 2-12	Example 2-13	Example 2-14
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)
	MOCA amine equivalent (%)
	Ketimine (weight g)		1.660
	Ketimine amine equivalent (%) (*1)		1.16
	catalyst	DETDA	0.0083		0.0050		0.0913
		Bz-Cl		0.0083		0.0050	0.0913
Curing speed (time to reach 100,000 cPs)			56'05"	60'11"	58'55"	63'55	61'06"
Hardness after 1 day (Shore A)			47	45	39	37	62
Hardness after 3 days (Shore A)			68	65	58	57	84

<Physical property evaluation method>

(*1) ketamine amine equivalent (%) = used ketamine used weight / ketamine amine molar equivalent (143.1) * 100

(*2) In order to compare the performance of MOCA and ketamine, the amine equivalents (%) of MOCA and ketamine were equally compared to 1.16.

<Results of physical property evaluation>

Example 2, as in Example 1, the curing rate, 1 day and 3 days after looking at the hardness data, compared with MOCA, when converting to parts by weight of ketamine per 100 parts by weight of the catalyst for controlling the hardness DETDA or catalyst for controlling the curing rate of benzyl chloride (Bz -Cl) Examples 1-1 to 2-11 containing 0.5 to 10 parts by weight of one or more components of Comparative Example MOCA when using the curing rate and the hardness and the deviation from the hardness shows a similar result within 10%, respectively, low-toxic chain extender composition It was found that it can be used as a substitute for phosphorus MOCA.

(Example 3)

3.24 weight g (1.16 amine equivalent (%) (amine molar equivalent 279.3) of polyaspartic ester (PAE) synthesized from diethyl maleate (DEM) and isophorone diamine (IPDA) at 100 g of main part and 70 g of curing agent) Polyurethane synthesized in the same manner as in Example 1 using a chain extender mixed with 0.0097 to 0.1782 g of DETDA for hardness control and 0.0097 to 0.1782 g of benzyl chloride for controlling curing rate as a catalyst The properties of the polymer are shown in [Table 3].

Since the molecular weight of PAE mentioned in Example 3 is 558.6 and the number of amine groups in the molecule is two, the amine molar equivalent of this PAE is 279.3.

The evaluation method of physical properties is the same as in Example 1.

division			Comparative example	Example 3-1	Example 3-2	Example 3-3	Example 3-4
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)		1.55
	MOCA amine equivalent (%)		1.16
	PAE (weight g)			3.240
	PAE amine equivalent (%) (*1)			1.16
	catalyst	DETDA (weight g)		0.1620	0.1620	0.1620	0.0972
		Bz-Cl (weight g)		0.1620	0.0972	0.0162	0.1620
Curing speed (time to reach 100,000 cPs)			58'35"	57'35"	56'30"	53'50"	61'23"
Hardness after 1 day (Shore A)			50	53	54	55	45
Hardness after 3 days (Shore A)			71	72	74	76	70
division			Example 3-5	Example 3-6	Example 3-7	Example 3-8	Example 3-9
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)
	MOCA amine equivalent (%)
	PAE (weight g)		3.240
	PAE amine equivalent (%) (*1)		1.16
	catalyst	DETDA (weight g)	0.0972	0.0972	0.0162	0.0162	0.0162
		Bz-Cl (weight g)	0.0972	0.0162	0.1620	0.0972	0.0162
Curing speed (time to reach 100,000 cPs)			60'45"	58'05"	63'11"	62'25"	60'37"
Hardness after 1 day (Shore A)			50	52	45	46	46
Hardness after 3 days (Shore A)			71	72	65	67	69
division			Example 3-10	Example 3-11	Example 3-12	Example 3-13	Example 3-14
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)
	MOCA amine equivalent (%)
	PAE (weight g)		3.240
	PAE amine equivalent (%) (*1)		1.16
	catalyst	DETDA (weight g)	0.0162		0.0097		0.1782
		Bz-Cl (weight g)		0.0162		0.0097	0.1782
Curing speed (time to reach 100,000 cPs)			57'58"	62'48"	64'04"	66'54"	60'54"
Hardness after 1 day (Shore A)			45	45	41	38	63
Hardness after 3 days (Shore A)			67	64	60	57	84

<Physical property evaluation method>

(*1) PAE amine equivalent (%) = PAE used weight / PAE amine molar equivalent * 100

(*2) To compare the performances of MOCA and PAE, the amine equivalents (%) of MOCA and PAE were equally compared to 1.16%.

<Results of physical property evaluation>

Example 3 and Example 1 and Example 2, the curing rate, 1 day and 3 days after looking at the hardness data compared to the MOCA in terms of parts by weight compared to the polyaspartic ester (PAE) hardness control catalyst per 100 parts by weight or Examples 3-1 to 3-11 containing 0.5 to 10 parts by weight of one or more components of the catalyst for controlling the curing rate exhibited similar results within 10% of variation in curing rate and hardness when using MOCA, which is a comparative example. It was found that the composition can be used as a substitute for MOCA.

(Example 4)

100 parts by weight of the main part and 70 parts by weight of the curing agent, 1.06% by weight g (0.74 amine equivalents (%) (amine molar equivalents 143.3)) of aldimine synthesized from diethyl toluenediamine (DETDA) and isobutyl aldehyde, and IPDA and diethyl maleate Synthesized from polyaspartic ester (PAE) 1.173 weight g (0.42 amine equivalent (%) (amine molar equivalent 279.3)) as a catalyst DETDA 0.0067 to 0.1228 weight g and benzyl chloride 0.0067 to 0.1228 weight g alone or by mixing Example The properties of the polyurethane polymer synthesized in the same manner as 1 are shown in [Table 4].

Since the molecular weight of the aldimine mentioned in Example 4 is 286.6 and the number of amine groups in the molecule is two, the amine molar equivalent of this aldimine is 143.3, and in the case of polyaspartic ester (PAE), the molecular weight is 558.6 and the number of amine groups in the molecule Since there are two, the molar equivalent of amine in this PAE is 279.3.

The evaluation method of physical properties is the same as in Example 1.

division			Comparative example	Example 4-1	Example 4-2	Example 4-3	Example 4-4
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)		1.55
	MOCA amine equivalent (%)		1.16
	Aldimine (weight g)			1.060
	Aldimineamine equivalent (%) (*1)			0.740
	PAE (weight g)			1.173
	PAE amine equivalent (%) (*2)			0.420
	catalyst	DETDA (weight g)		0.1117	0.1117	0.1117	0.0670
		Bz-Cl (weight g)		0.1117	0.0670	0.0112	0.1117
Curing speed (time to reach 100,000 cPs)			58'35"	57'00"	55'55"	54'10"	63'18"
Hardness after 1 day (Shore A)			50	53	54	55	45
Hardness after 3 days (Shore A)			71	72	74	77	70
division			Example 4-5	Example 4-6	Example 4-7	Example 4-8	Example 4-9
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)
	MOCA amine equivalent (%)
	Aldimine (weight g)		1.060
	Aldimineamine equivalent (%) (*1)		0.740
	PAE (weight g)		1.173
	PAE amine equivalent (%) (*2)		0.420
	catalyst	DETDA (weight g)	0.0670	0.0670	0.0112	0.0112	0.0112
		Bz-Cl (weight g)	0.0670	0.0112	0.1117	0.0670	0.0112
Curing speed (time to reach 100,000 cPs)			62'30"	59'17"	63'40"	61'53"	60'03"
Hardness after 1 day (Shore A)			46	48	45	47	48
Hardness after 3 days (Shore A)			70	71	65	67	68
division			Example 4-10	Example 4-11	Example 4-12	Example 4-13	Example 4-14
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)
	MOCA amine equivalent (%)
	Aldimine (weight g)		1.060
	Aldimineamine equivalent (%) (*1)		0.740
	PAE (weight g)		1.173
	PAE amine equivalent (%) (*2)		0.420
	catalyst	DETDA (weight g)	0.0112		0.0067		0.1228
		Bz-Cl (weight g)		0.0112		0.0067	0.1228
Curing speed (time to reach 100,000 cPs)			58'16"	62'22"	63'40	66'30	61'35"
Hardness after 1 day (Shore A)			46	45	40	38	64
Hardness after 3 days (Shore A)			66	64	59	58	84

<Physical property evaluation method>

(*1) Aldimine amine equivalent (%) = total amount of used aldimine used / Aldimine amine molar equivalent * 100

(*2) PAE amine equivalent (%) = used PAE used weight / PAE amine molar equivalent * 100

(*3) In order to compare the performance of MOCA, aldimine and PAE mixtures, the sum of the aldimine amine equivalents (0.74%) and PAE amine equivalents (0.42%) was set to 1.16%, which is the same as the MOCA amine equivalent (%). Compared.

<Results of physical property evaluation>

Example 4 also in Example 1 to Example 3, the curing rate, 1 day and 3 days after looking at the hardness data, compared with the comparative example MOCA, when converted to parts by weight of adimine and polyaspartic ester (PAE) mixed with each other Deviation from the curing rate and hardness when using MOCA of Examples 4-1 to 4-11 of Examples 4-1 to 4-11 including 0.5 to 10 parts by weight of at least one component of a catalyst for controlling hardness or a catalyst for controlling curing rate per 100 parts by weight is within 10%, respectively. By showing similar results, it was found that it can be used as a substitute for MOCA, a low toxicity chain extender composition.

(Example 5)

100 parts by weight of the main part and 70 parts by weight of the curing agent, 1.059 parts by weight of ketamine synthesized from diethyl toluene diamine (DETDA) and methyl ethyl ketone (0.740 amine equivalents (%) (amine molar equivalent 143.1)) and diethyl DETDA 0.0067 to 0.1228 wtg and benzyl chloride as catalyst for 1.173 wtg (0.420 amine equivalent (%) (amine molar equivalent 279.3)) of polyaspartic ester (PAE) synthesized from maleate (DEM) and isophorone diamine (IPDA) (Bz-Cl) The physical properties of the polyurethane polymer synthesized by using 0.0067 to 0.1228 weight g alone or by mixing are shown in [Table 5].

Since the molecular weight of ketamine mentioned in Example 5 is 286.2 and the number of amine groups in the molecule is 2, the amine molar equivalent of this ketimine is 143.1, and in the case of PAE, the molecular weight is 558.6 and the number of amine groups in the molecule is 2, so this PAE The molar equivalent of amine is 279.3.

The evaluation method of physical properties is the same as in Example 1.

division			Comparative example	Example 5-1	Example 5-2	Example 5-3	Example 5-4
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)		1.55
	MOCA amine equivalent (%)		1.16
	Ketimine (weight g)			1.059
	Ketiminamine equivalent (%) (*1)			0.740
	PAE (weight g)			1.173
	PAE amine equivalent (%) (*2)			0.420
	catalyst	DETDA		0.1116	0.1116	0.1116	0.0670
		Bz-Cl		0.1116	0.0670	0.0112	0.1116
Curing speed (time to reach 100,000 cPs)			58'35"	56'40"	55'38"	53'52"	63'00"
Hardness after 1 day (Shore A)			50	52	54	55	45
Hardness after 3 days (Shore A)			71	73	75	77	70
division			Example 5-5	Example 5-6	Example 5-7	Example 5-8	Example 5-9
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)
	MOCA amine equivalent (%)
	Ketimine (weight g)		1.058
	Ketiminamine equivalent (%) (*1)		0.740
	PAE (weight g)		1.173
	PAE amine equivalent (%) (*2)		0.420
	catalyst	DETDA	0.0670	0.0670	0.0112	0.0112	0.0112
		Bz-Cl	0.0670	0.0112	0.1116	0.0670	0.0112
Curing speed (time to reach 100,000 cPs)			62'12"	59'01"	63'23"	61'30"	59'40"
Hardness after 1 day (Shore A)			46	47	45	46	48
Hardness after 3 days (Shore A)			71	72	66	68	70
division			Example 5-10	Example 5-11	Example 5-12	Example 5-13	Example 5-14
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)
	MOCA amine equivalent (%)
	Ketimine (weight g)		1.058
	Ketiminamine equivalent (%) (*1)		0.740
	PAE (weight g)		1.173
	PAE amine equivalent (%) (*2)		0.420
	catalyst	DETDA	0.0112		0.0067		0.1228
		Bz-Cl		0.0112		0.0067	0.1228
Curing speed (time to reach 100,000 cPs)			57'57"	62'05"	60'30	66'53	60'14"
Hardness after 1 day (Shore A)			48	45	40	39	64
Hardness after 3 days (Shore A)			68	66	60	57	85

<Physical property evaluation method>

(*1) ketamine amine equivalent (%) = total used ketamine weight used / ketamine amine molar equivalent * 100

(*2) PAE amine equivalent (%) = used PAE used weight / PAE amine molar equivalent * 100

(*3) To compare the performance of MOCA, ketamine and PAE mixtures, the sum of ketamine amine equivalents (%) and PAE amine equivalents (%) was compared with MOCA amine equivalents (%) to be 1.16%. .

<Results of physical property evaluation>

Example 5 is similar to Example 1 to Example 4, the curing rate, 1 day and 3 days after looking at the hardness data, compared to MOCA, when mixed in parts by weight, ketamine and polyaspartic ester (PAE) 100 weights mixed together Similar results with less than 10% variation in cure rate and hardness when using MOCA of Examples 5-1 to 5-11 of Examples 5-1 to 5 parts by weight containing at least 0.5 to 10 parts by weight of one or more components of a catalyst for controlling hardness per part or a catalyst for controlling curing rate It was found that it can be used as a substitute for MOCA, a low-toxic chain extender composition.

(Example 6)

10030 g of main part and 70 wt. of curing agent, 0.530 wt.g (0.370 amine equivalents (%) (amine molar equivalents 143.3)) of Aldimine synthesized from diethyltoluenediamine (DETDA) and isobutylaldehyde as chain extenders, DETDA and methyl 0.530 wt g of ketamine synthesized from ethyl ketone (0.370 amine equivalent (%) (amine molar equivalent 143.1)) and 1.173 wt g of PAE synthesized from IPDA and diethyl maleate (0.420 amine equivalent (%) (amine molar equivalent 279.3)) As a catalyst, the properties of the polyurethane polymer synthesized by using DETDA 0.0070 to 0.1283 wt g and benzyl chloride (Bz-Cl) 0.0070 to 0.1283 wt g alone or in combination are as shown in [Table 6].

Since the molecular weight of the aldimine mentioned in Example 6 is 286.6 and the number of amine groups in the molecule is 2, the amine molar equivalent of this aldimine is 143.3, the molecular weight of ketamine is 286.2, and the number of amine groups in the molecule is 2, so the amine molar equivalent of this ketimine Is 143.1, and in the case of PAE, the molecular weight is 558.6 and the number of amine groups in the molecule is two, so the molar equivalent of amine in this PAE is 279.3.

The evaluation method of physical properties is the same as in Example 1.

division			Comparative example	Example 6-1	Example 6-2	Example 6-3	Example 6-4
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)		1.55
	MOCA amine equivalent (%)		1.16
	Aldimine (weight g)			0.530
	Aldimineamine equivalent (%) (*1)			0.370
	Ketimine (weight g)			0.530
	Ketiminamine equivalent (%) (*2)			0.370
	PAE (weight g)			1.173
	PAE amine equivalent (%) (*3)			0.420
	catalyst	DETDA		0.1167	0.1167	0.1167	0.0670
		Bz-Cl		0.1167	0.0670	0.0117	0.1167
Curing speed (time to reach 100,000 cPs)			58'35"	56'51"	55'51"	54'02"	63'10"
Hardness after 1 day (Shore A)			50	52	54	55	45
Hardness after 3 days (Shore A)			71	73	74	76	70
division			Example 6-5	Example 6-6	Example 6-7	Example 6-8	Example 6-9
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)
	MOCA amine equivalent (%)
	Aldimine (weight g)		0.530
	Aldimineamine equivalent (%) (*1)		0.370
	Ketimine (weight g)		0.530
	Ketiminamine equivalent (%) (*2)		0.370
	PAE (weight g)		1.173
	PAE amine equivalent (%) (*3)		0.420
	catalyst	DETDA	0.0670	0.0670	0.0117	0.0117	0.0117
		Bz-Cl	0.0670	0.0117	0.1167	0.0670	0.0117
Curing speed (time to reach 100,000 cPs)			62'23"	59'11"	63'35"	61'41"	59'49"
Hardness after 1 day (Shore A)			46	47	45	46	47
Hardness after 3 days (Shore A)			71	72	65	67	69
division			Example 6-10	Example 6-11	Example 6-12	Example 6-13	Example 6-14
Main part (weight g)			100
Curing agent (weight g)			70
Chain extender	MOCA (weight g)
	MOCA amine equivalent (%)
	Aldimine (weight g)		0.530
	Aldimineamine equivalent (%) (*1)		0.370
	Ketimine (weight g)		0.530
	Ketiminamine equivalent (%) (*2)		0.370
	PAE (weight g)		1.173
	PAE amine equivalent (%) (*3)		0.420
	catalyst	DETDA	0.0117		0.0070		0.1283
		Bz-Cl		0.0117		0.0070	0.1283
Curing speed (time to reach 100,000 cPs)			58'10"	62'20"	64'08"	66'48"	60'34"
Hardness after 1 day (Shore A)			48	45	40	39	63
Hardness after 3 days (Shore A)			68	65	60	58	85

<Physical property evaluation method>

(*1) Aldimine amine equivalent (%) = total amount of used aldimine used / Aldimine amine molar equivalent * 100

(*2) ketamine amine equivalent (%) = total used ketamine weight used / ketamine amine molar equivalent * 100

(*3) PAE amine equivalent (%) = PAE used weight / PAE amine molar equivalent * 100

(*4) In order to compare the performances of MOCA, aldimine, and ketamine and PAE mixtures, the sum of aldimine amine equivalents (%), ketamine amine equivalents (%) and PAE amine equivalents (%) is the amine equivalent of MOCA ( %) was compared to 1.16%.

<Results of physical property evaluation>

Example 6 is similar to Example 1 to Example 5, the curing rate, 1 day and 3 days after looking at the hardness data compared to MOCA compared with each other in terms of parts by weight of mixed adimine, ketamine and polyaspartic ester (PAE ) Deviation from the cure rate and hardness when using MOCA of Examples 6-1 to 6-11, which include 0.5 to 10 parts by weight of at least one component of a catalyst for controlling hardness or a catalyst for controlling curing speed per 100 parts by weight, is 10%, respectively. As a result of the similar results, it was found that it can be used as a substitute for MOCA, a low-toxic chain extender composition.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of the process of those skilled in the art using the basic concept of the present invention defined in the following claims are also provided. It belongs to the scope of the invention.

Claims (8)

1. 0.5 to 10 parts by weight of at least one component selected from a catalyst for controlling hardness and a catalyst for controlling a curing rate per 100 parts by weight of at least one component selected from aldimine, ketamine and polyaspartic ester

   Containing

   Chain extender composition for polyurethane.
2. In claim 1,

   The adimine is prepared by the reaction of aldehyde and amine,

   The ketamine is prepared by the reaction of ketone and amine,

   The polyaspartic ester is prepared by the reaction of an alkenyl ester and an amine

   Chain extender composition for polyurethane.
3. In claim 2,

   The aldehyde

   It is a mixture of one or two or more selected from formaldehyde, acetaldehyde, paraformaldehyde, propionaldehyde, benzaldehyde, butylaldehyde, isobutylaldehyde and 2-ethylhexanaldehyde.

   Chain extender composition for polyurethane.
4. In claim 2,

   The ketone

   Acetone, methyl ethyl ketone, methyl butyl ketone, cyclohexanone, methyl isobutyl ketone, isophorone and acetophenone, mixtures of one or more.

   Chain extender composition for polyurethane.
5. In claim 2,

   The alkenyl ester is

   A mixture of one or two or more selected from dialkyl maleates and dialkyl fumarates

   Chain extender composition for polyurethane.
6. In any one of claims 3 to 5,

   Isophoronediamine, polyoxypropylenediamine, polyoxypropylenetriamine, methanediamine, 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,3-diaminopentane, 1, 5-diaminomethylpentane, 1,3- and 1,4-xylenediamine, 1,6-hexamethylenediamine, phenylenediamine, tolylenediamine, bis(4-aminophenyl)methane, bis(4-aminocyclo Hexyl)methane, 1,2-, 1,3- and 1,4-diaminocyclohexane, 2,4- and 2,6-diethyltoluenediamine (DETDA), 2,4- and 2,6-dimethyl One or more mixtures selected from toluenediamine

   Chain extender composition for polyurethane.
7. In claim 1,

   The curing rate control catalyst

   Organic acids such as benzoic acid or oxalic acid,

   Aromatic chlorides that are benzene chloride or benzyl chloride (Bz-Cl),

   Inorganic acid selected from hydrochloric acid, sulfuric acid and phosphoric acid, and

   Chloride and chlorine oxides containing sulfur or phosphorus

   A mixture of one or more selected from

   Chain extender composition for polyurethane.
8. In claim 1,

   The hardness control catalyst

   Isophoronediamine, methanediamine, 1,2-ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, 1,3-diaminopentane, 1,5-diaminomethylpentane, 1,3- And 1,4-xylenediamine, 1,6-hexamethylenediamine, phenylenediamine, tolylenediamine, bis(4-aminophenyl)methane, bis(4-aminocyclohexyl)methane, 1,2-, 1, 3- and 1,4-diaminocyclohexane, 2,4- and 2,6-diethyltoluenediamine (DETDA), 2,4- and 2,6-dimethyltoluenediamine (DMTDA), phenalcarmine, melamine , Huntsman's Jeffamine D-230, Jeffamine D-2000, Jeffamine D-5000 and Jeffamine T-403

   Chain extender composition for polyurethane.