KR101284152B1 - Silicon copolymer, its manufacturing method and fabric softner using the same - Google Patents

Abstract

PURPOSE: An amino-modified silicon copolymer is provided to provide excellent touch-feeling, flexibility, salt removal, and moisture-absorption properties, and to be self-emulsified just by a single addition. CONSTITUTION: An amino-modified silicon copolymer is formed by a ring-opening copolymerization of a branched epoxy polyalkylene oxide-modified silicon compound represented by chemical formula 1: [R^1_3Si[ (SiO (R^1)_2)_x (SiO (R^1R^2 (C)aH_2aO)_bH)_y (SiO (R^1R^3X))_z]SiR^1_3, and an amino compound represented by chemical formula 3: [ZR^4Z]. In the chemical formulas: R^1 is C1-4 alkyl group; each of R^2 and R^3 is a divalent C1-10 hydrocarbon group; R^4 is a C2-10 divalent hydrocarbon group, or polyalkyleneoxide represented by formula: [O (C_aH_2aO)_b]; and X is a divalent organic group formed by epoxide ring opening. [Reference numerals] (S11) Manufacture a side chain epoxy/polyalyene oxide-modified polysiloxane by the reaction of a side chain hydrogen polysiloxane which simultaneously has an epoxy group and an polyalkylene oxide group under the presence of a platinum catalyst; (S12) Carry out a copolymerization reaction through an epoxy opening reaction by both terminal-amino compounds, by reacting the side chain epoxy/polyalkylene oxide-modified polysiloxane and the both terminal-amino compounds under the presence of a solvent

Description

Amino-modified silicone copolymer having excellent hygroscopicity and self-emulsification, a manufacturing method thereof, and a fabric softener using the silicone copolymer {Silicon Copolymer, its Manufacturing Method and Fabric Softner Using the Same}

The present invention relates to an amino-modified silicone copolymer having excellent hygroscopicity and excellent self-emulsification, and more particularly, epoxy ring opening reaction of an epoxy polyalkylene oxide-modified silicone compound and a sock end epoxy compound using a sock end amine. It relates to a method for producing a random block copolymer wherein the polyalkylene oxide modified silicone compound is formed through an epoxy bond ring-opened by an amine. The amine of the prepared block copolymer is quaternized to give excellent hygroscopicity, and since it contains hydrophilic polyalkylene oxide, self-emulsification is possible with only a single addition, and it can provide excellent touch, flexibility, reinflammability, and hygroscopicity when treating fibers. .

U. S. Patent 4,242, 466 discloses siloxane-polyalkylene oxide copolymers of type (AB) nA, ie block copolymers in which siloxanes and polyethers are alternated.

U. S. Patent No. 4,833, 225 also discloses (AB) nA type silicone amino oils derived from low molecular weight diamines having amino end groups and polysiloxanes blocked with epoxy ends.

Korean Patent Application Publication No. 1997-707826 recounts non-hydrolyzable, block (AB) nA type copolymers and these copolymers in alternating units of polysiloxanes and amino-polyalkylene oxides.

However, the silicone amino oils disclosed in this related art show an alternating block copolymer of (AB) n by reacting an amine at the epoxy end. Hydrogen sock-end silicone polymer is used as a starting material in the production of epoxy-terminated silicone polymer, but the disadvantage is that raw materials are expensive because raw materials are expensive. In addition, when the epoxy is substituted at the end, the substitution rate is not good, and the silicone residue which cannot be bonded with the aminoalkylene oxide is not self-emulsified. .

In addition, European Patent EP2027328A1 discloses a block copolymer in which an amide group is introduced into silicone, but there is a disadvantage of yellowing possibility when treating fibers due to yellowing due to an acid base reaction.

Korean Patent Application Publication No. 10-2003-7014806 discloses a non-hydrolyzable, block copolymer composed of alternating units by combining polysiloxane and sock-end epoxy polyalkylene oxide with an amine, and quaternizing the amine to impart hygroscopicity. It was.

However, the preparation is not able to secure the self-emulsification can be used only by mixing the emulsifier.

Therefore, the present invention provides excellent hygroscopicity due to quaternization, and pre-reacts polyalkylene oxide to polysiloxane, which is excellent in reinflammability, strong in alkaline solution, and low in crosslinking potential. There is an urgent need for the development of amine-polyalkylene oxide copolymer production techniques for possible fiber treatment.

US 4,242,466 B1 US 4,833,225 B1 KR 10-1997-707826 A1 EP 2027328 A1 KR 10-2003-7014806 A1

The problem to be solved by the present invention is to provide a modified silicone copolymer having good hygroscopicity, flexibility, no saponification and gelation, excellent reinflammability, a preparation method thereof and a fabric softener comprising the same.

In order to achieve the technical problem to be achieved by the present invention, the side chain epoxy polyalkylene oxide modified silicone compound of Formula 1 and the sock end amino compound of Formula 3 is formed by a copolymerization reaction through an epoxy ring opening reaction with an amine, An amino modified silicone copolymer is characterized in that formula (2) optionally participates in the copolymerization reaction.

In the above formula

R ¹ is an alkyl group containing 1 to 4 carbon atoms, R ² , R ³ Each independently a divalent hydrocarbon group containing 1 to 10 carbon atoms, and R ⁴ is a divalent hydrocarbon group containing 2 to 10 carbon atoms, or a poly group that can be represented by [O (C _a H _2a O) _c ] Alkylene oxide, X, Y are independently a divalent organic group formed by epoxide ring opening, -CH2CH (OH) (CH2) vCH (OH) CH2-, -CH [CH2OH] (CH2) vCH [CH2OH ]-, -CH2CH (OH) (CH2) vCH [CH2OH]-,-(CH2) v-OCH2CH (OH) CH2-, where v is 2 to 6 and Z is an amine group It contains primary, secondary and tertiary amines, a is a positive integer from 2 to 4, preferably 2 to 3, b is a positive integer from 0 to 100, and x is from 1 to 500 Is a positive integer, y is a positive integer from 1 to 300, z is a positive integer from 1 to 3

Amine Z of Formula 3 is a primary or secondary amine group; X and Y in Formulas 1 and 2 are epoxide groups, and the epoxide group in the copolymerization reaction is -CH2CH (OH) (CH2) vCH (OH) CH2-, -CH [CH2OH] (CH2) vCH [CH2OH] At least one structure selected from-, -CH2CH (OH) (CH2) vCH [CH2OH]-and-(CH2) v-OCH2CH (OH) CH2-, wherein v is an amount of 2 to 6 It is preferable that it is an integer of.

It is preferable that Z> X + Y is a reaction in which X and Y, each of the epoxy groups of Formulas 1 and 2, are randomly bonded to each other by a ring-opening reaction by Z which is the amine group of Formula 3 above. Z must be greater than the sum of the epoxy groups X and Y in the amine group to produce a compound in which the amine group may exist at the terminal. Primary amine groups can react with epoxy groups at 1: 1 or 1: 2, and secondary amine groups can react with epoxy groups at 1: 1. Therefore, when preparing a compound having an amine group at the end, it is preferable that the number of amine groups should be larger than the number of epoxy groups.

The epoxide group X is selected from an allyl glycidyl ether group and an allyl epoxycyclohexyl group, and the epoxide group Y is a glycidyl ether group, an epoxycyclohexyl alkylene group, w- (3,4) -epoxy It is preferably selected from cyclohexylalkylene, b- (3,4-epoxycyclohexyl) -b-methylethylene, or b- (3,4-epoxy-4-methylcyclohexyl) -b-methylethylene Do.

In Formula 2, the polyalkylene oxide compound represented by (C _a H _2a O) is composed of ethylene oxide (a = 2), propylene oxide (a = 3) in random or block form, or ethylene oxide (a = 2) It is preferable that it is comprised independently.

It is preferable that the amine group connected by the said amine group Z is protonated or quaternized.

It is preferable that the sockdan amino compound of Formula 3 is selected from hydrocarbon diamine or polyalkylene oxide diimine.

The hydrocarbon diamine is preferably selected from ethylene diamine, propylene diamine, butylene diamine, hexylene diamine.

In order to achieve the technical problem to be achieved by the present invention, (A) a side chain hydrogen polysiloxane having an epoxy group and a polyalkylene oxide group at the same time by reacting under a predetermined catalyst to prepare a side chain epoxy polyalkylene oxide modified polysiloxane of formula (1) step; And (B) reacting the side chain epoxy polyalkylene oxide-modified polysiloxane with the sock end amino compound of Formula 3 under a predetermined solvent, thereby performing a copolymerization reaction through an epoxy ring opening reaction with an amine of the sock end amino compound of Formula 3 It provides a method of producing an amino-modified silicone copolymer comprising a; step to occur.

[Formula 1]

[R ¹ ₃ Si [(SiO (R ¹ ) ₂ ) _x (SiO (R ¹ R ² (C _a H _2a O) _b H) _y (SiO (R ¹ R ³ X)) _z ] SiR ¹ ₃

(3)

[ZR ⁴ Z]

In the above formula

R ¹ is an alkyl group containing 1 to 4 carbon atoms,

R ² , R ³ Each independently a divalent hydrocarbon group containing 1 to 10 carbon atoms,

R ⁴ is a divalent hydrocarbon group containing 2 to 10 carbon atoms or _a polyalkylene oxide represented by [O (C _a H _2a O) _c ],

X is a divalent organic group formed independently by epoxide ring opening, and is -CH2CH (OH) (CH2) vCH (OH) CH2-, -CH [CH2OH] (CH2) vCH [CH2OH]-, -CH2CH (OH ) (CH2) vCH [CH2OH]-,-(CH2) v-OCH2CH (OH) CH2-,

Where v is 2 to 6,

Z is an amine group containing primary, secondary and tertiary amines,

a is a positive integer of 2 to 4, preferably 2 to 3, b is a positive integer of 0 to 100, x is a positive integer of 1 to 500, y is a positive integer of 1 to 300 Z is a positive integer from 1 to 3

In the above formula, R ¹ is an alkyl group containing 1 to 4 carbon atoms, R ² , R ³ Each independently a divalent hydrocarbon group containing 1 to 10 carbon atoms, and R ⁴ is a divalent hydrocarbon group containing 2 to 10 carbon atoms, or a poly group that can be represented by [O (C _a H _2a O) _c ] Alkylene oxide, X is independently a divalent organic group formed by epoxide ring opening, -CH2CH (OH) (CH2) vCH (OH) CH2-, -CH [CH2OH] (CH2) vCH [CH2OH]- , -CH2CH (OH) (CH2) vCH [CH2OH]-,-(CH2) v-OCH2CH (OH) CH2-, where v is 2 to 6 and Z is the primary group with an amine group , Secondary, tertiary amine, a is a positive integer of 2 to 4, preferably 2 to 3, b is a positive integer of 0 to 100, x is a positive of 1 to 500 Is an integer, y is a positive integer from 1 to 300, and z is a positive integer from 1 to 3.

(C) after the step (B), the step of adding the stepped epoxy polyoxyalkylene composition of the formula (2); preferably further comprises.

 [Formula 2]

[YO (C _a H _2a O) _b Y]

Y is independently a divalent organic group formed by epoxide ring opening, -CH2CH (OH) (CH2) vCH (OH) CH2-, -CH [CH2OH] (CH2) vCH [CH2OH]-, -CH2CH (OH ) (CH2) vCH [CH2OH]-,-(CH2) v-OCH2CH (OH) CH2-.

(D) after the step (C), further comprising the step of further adding a side chain epoxy polyalkylene oxide modified polysiloxane of the formula (1).

(E) quaternizing the product of step (B); preferably further comprises.

Preferably, the side chain hydrogen polysiloxane is a partial side chain hydrogen polysiloxane.

Wherein the side chain epoxy polyalkylene oxide modified polysiloxane is to pre-react the polyalkylene oxide to the partial hydrogen polysiloxane to secure the self-emulsification to the silicone compound in advance, the step (B) after the pre-reaction It is preferable that it is carried out.

The catalyst is a platinum catalyst, the solvent is preferably any one of alcohol or a mixed solvent of alcohol and water.

In order to achieve the technical problem to be achieved by the present invention, it provides a fabric softener composition comprising the amino-modified silicone copolymer.

The random amino modified silicone copolymer of the present invention has the following effects.

First, the amino modified silicone copolymer of the present invention provides excellent hygroscopicity by quaternization of amines, and includes hydrophilic polyalkylene oxide, which enables self-emulsification with only a single addition. Can provide.

Second, the amino-modified silicone copolymer of the present invention copolymerizes the pre-reacted silicone-Epoxy / EOPO copolymer with the sockdan amine, thereby controlling various functional group contents, and is relatively a gum-up phenomenon with the self-emulsification secured in advance. Can be free.

Third, the amino-modified silicone copolymer of the present invention can maximize the self-emulsification by quaternizing the amine group sufficiently secured, it is possible to impart excellent hygroscopicity during fiber treatment.

The present invention also provides use as a softener comprising the copolymer, in particular as a non-polluting fiber softener.

1 is an exemplary manufacturing method for the silicone copolymer of the present invention.
Figure 2 is another embodiment of the preparation method for the silicone copolymer of the present invention.

Hereinafter, the present invention will be described in detail.

The present invention is modified with a side chain epoxy polyalkylene oxide modified formula of the formula (1) (modified epoxy and polyalkylene oxide in the silicon compound, respectively, as follows). Copolymerization of polysiloxane with the sock end amino compound of formula (3), The addition of the sock end epoxy compound of Formula 2 provides a random block copolymer using an epoxy ring-opening reaction with an amine.

[Formula 1]

[R ¹ ₃ Si [(SiO (R ¹ ) ₂ ) _x (SiO (R ¹ R ² (C _a H _2a O) _b H) _y (SiO (R ¹ R ³ X)) _z ] SiR ¹ ₃

[Formula 2]

[YO (C _a H _2a O) _b Y]

(3)

[ZR ⁴ Z]

In the above formula

R ¹ is an alkyl group containing 1 to 4 carbon atoms, preferably a methane group having 1 carbon atom;

R ² , R ³ Each independently a divalent hydrocarbon group containing 1 to 10 carbon atoms, preferably a propylene group having 3 carbon atoms;

R ⁴ is a divalent hydrocarbon group containing 2 to 10 carbon atoms, preferably 2 to 3 alkyl groups; A polyalkylene oxide group represented by [O (C _a H _2a O) _c ], preferably an amino polyalkylene oxide having a molecular weight of 500 to 2000;

X and Y are independently a divalent organic group formed by epoxide ring opening, and are independently -CH2CH (OH) (CH2) vCH (OH) CH2-, -CH [CH2OH] (CH2) vCH [CH2OH]-,- CH2CH (OH) (CH2) vCH [CH2OH]-,-(CH2) v-OCH2CH (OH) CH2- is selected from the crowd consisting of

Where v is 2 to 6

Z is an amine and includes primary, secondary and tertiary amines.

a is a positive integer of 2 to 4, preferably 2 to 3, b is a positive integer of 0 to 100, x is a positive integer of 1 to 500, y is a positive integer of 1 to 300 And z is a positive integer of 1 to 3.

In the present invention, X in Chemical Formula 1 is introduced by reacting hydrogen polysiloxane with an epoxy compound having an olefin group capable of addition reaction; Take the following example.

Examples of the polyalkylene oxide compound having an epoxy at the sock end of Formula 2 may include the following compounds, but are not limited thereto.

In addition, examples of the compound having an amine at the sock end of Formula 3 may include the following compounds, but are not limited thereto.

In the present invention, the following Chemical Formula 11 may be induced by combining the Chemical Formula 1 and Chemical Formula 3, or optionally, adding the Chemical Formula 2 to the reaction. In order to dissolve well in water, the polyalkylene oxide and the content of Formula 1 and Formula 2 should have a value relative to silicon. Preferably, the total copolymer should have a hydrophilic polyalkylene oxide content of 20 to 50% by weight, and if it is more than that, it is well soluble in water due to the high hydrophilic group, but it is difficult to secure flexibility due to the low relative silicone content. There is this. In addition, when the hydrophilic polyalkylene oxide content is 20% by weight or less, it is difficult to dissolve in water, and thus self-emulsification cannot be secured.

Another important factor in controlling the properties of the copolymer may be the difference in degree of polymerization depending on the total amine and epoxy groups. Here, the amine group Z must be larger than the sum of X and Y, which are epoxy groups, to synthesize a copolymer having an amine group at its terminal.

In Formula 11,

x is a positive integer from 1 to 500, y is a positive integer from 1 to 300, z is a positive integer from 1 to 3;

R4 is a divalent hydrocarbon group containing 2 to 10 carbon atoms, or _a polyalkylene oxide represented by [O (C _a H _2a O) _c ];

X 'and Y' are the ring-opened form of epoxide,

Z 'is a primary or secondary amine group,

m is a positive integer from 1 to 100,

n is a positive integer from 0 to 50;

m + n> 2.

In the case of the polysiloxane copolymer having an amino group as in the present invention, a strong physicochemical bond can be made with the hydrophilic group on the fiber surface by using a strong hydrogen bond of the amine group. It is generally known that the use of such strong hydrogen bonds to give the flexible surface properties of silicon to the fiber surface improves the high sensitivity of the fiber, softness, and the like.

In general, the higher the amine group is known to increase the flexibility of the fiber, in the case of the present invention, because the side chain hydrogen polysiloxane having a large number of reactors, there is an advantage that can control a very large amount of amine groups and polyalkylene oxide groups have.

In addition, the amine group is quaternized with hydrochloric acid, a substance such as methyl chloride, dimethylsulfonate, or methylchloroacetate to ensure excellent hygroscopicity during fiber treatment.

1 discloses a process for preparing an exemplary copolymer of the present invention.

In the copolymer of the present invention, a side chain hydrogen polysiloxane having an epoxy group and a polyalkylene oxide group at the same time is reacted under a predetermined catalyst to prepare a side chain epoxy polyalkylene oxide-modified polysiloxane of Formula 1 (S11) and the side chain epoxy poly Reacting the alkylene oxide-modified polysiloxane with the sock end amino compound of Formula 3 under a predetermined solvent, and performing a copolymerization reaction (S12) through an epoxy ring-opening reaction with an amine of the sock end amino compound of Formula 3; Can be prepared.

Figure 2 discloses another embodiment of the copolymer production method of the present invention.

The copolymer of the present invention comprises the step of reacting a side chain hydrogen polysiloxane having an epoxy group and a polyalkylene oxide group at the same time under a predetermined catalyst to prepare a side chain epoxy polyalkylene oxide modified polysiloxane (S21),

Reacting the side chain epoxy polyalkylene oxide-modified polysiloxane with the sock end amino compound of Formula 3 under a predetermined solvent to perform a copolymerization reaction (S22) through an epoxy ring-opening reaction with an amine of the sock end amino compound of Formula 3 Wow,

Adding the stepped epoxy polyoxyalkylene composition of Formula 2 (S23),

Reacting by further adding (S24) the side chain epoxy polyalkylene oxide-modified polysiloxane of Chemical Formula 1;

It may include performing a quaternization reaction of the amine (S25).

It will be described in more detail below.

Looking at an exemplary manufacturing process of the present invention, a step of preparing a partial side chain hydrogen silicone polymer by reacting a side chain hydrogen silicone polymer and a cyclosiloxane under an acid catalyst; Reacting the partially branched hydrogen silicone polymer with olefin epoxide and olefin polyalkylene oxide in a solvent to prepare an epoxy polyalkylene oxide-modified polysiloxane of Chemical Formula 1; And reacting with the sock end amino compound of Formula 1 and Formula 3 in a solvent while adding or without adding the sock end epoxy polyalkylene oxide compound of Formula 2 to the reaction.

In the first step, in order to synthesize polysiloxane having a certain ratio of side chain hydrogen functional groups, the side chain hydrogen polysiloxane and cyclosiloxane are reacted under an acid catalyst to have a hydrogen group of 0.2 to 2.3 mmol / g and a molecular weight of 500 to 10,000. It is manufactured to have.

In the second step, a copolymer capable of self-emulsifying by reacting at least two or more olefin epoxides in one molecule of the partially branched chain hydrogen polysiloxane synthesized in the first step and attaching all the remaining hydrogen groups and olefin alkylene oxide compounds Manufacture.

In the third step, the compound of formula (3) having a sockdan amine group is added to the epoxy ring-opening reaction by adding the formula (1) prepared in the second step in a solvent, and the sockdan polyalkylene oxide compound of the formula (2) is added or not added. And molecular weight and polyalkylene oxide content.

In the fourth step, the hygroscopicity is controlled by quaternization or protonation of the amine group.

When the self-emulsifying amino silicone block copolymer is prepared by the production method according to the present invention, the polysiloxane to be polymerized is previously reacted with a polyalkylene oxide, which is a hydrophilic group, and thus, even if unreacted polysiloxane remains, it is self-emulsified to the fiber. There is an advantage to reduce the sense of foreign matter because it is not adsorbed. By pre-reacting polyalkylene oxide to polysiloxane to react with silicone compound and amino compound which have secured self-emulsification property of silicone compound in advance. Can be prevented. In addition, since the use of polysiloxane having a large number of reactors can introduce a very large amount of epoxy groups and hydrophilic groups has a feature that can control the high amine content.

The reaction is performed using an alcohol such as isopropyl alcohol or a solvent in which water, organic and inorganic particles can be properly mixed, or without solvent. After completion of the reaction, the solvent can be exchanged with non-flammable solvents such as water, propylene glycol, and dipropylene glycol. The reaction product may be separated by distillation of the solvent under atmospheric pressure or reduced pressure, and the separated reaction product may be a viscous oil or wax depending on the molecular weight and the alkylene oxide content of the copolymer.

Synthesis process of the production method of the present invention and its use will be described through the following examples, but the scope of the present invention is not limited thereto.

Example 1

In the first step, prepare a thermometer, electric stirrer, nitrogen bubbler, condenser and dropping funnel in a 1000 mL round bottom flask. 53 g of side chain hydrogen polysiloxane and 658 g of cyclosiloxane were added thereto, 7.21 g of acid clay, an acid catalyst, 10 g of hexamethyldisiloxane were added thereto, and the reaction mixture was maintained at 80 ° C. for 3 hours. After the filter, the mixture was distilled under reduced pressure to 150c to obtain a partial hydrogen side chain polysiloxane having a hydrogen group of 1.1 mmol / g and a viscosity of 200 cP.

In the second step, 400 g of partially hydrogenated side chain polysiloxane synthesized in the first step was added to a 2 L four-necked flask equipped with a stirrer, an addition funnel and a reflux condenser, and 737 g of isopropyl alcohol and 13.28 g of allylglycidyl ether were added thereto. Give and mix well. 5 ppm of platinum acid was added thereto, followed by heating at 80c for 2 hours, and then 324.4 g of allyl polyalkylene oxide (AAE-1104, IC chemical) was added. After confirming the disappearance, the reaction was terminated to obtain a branched epoxy polyalkylene oxide-modified polysiloxane 50% isopropyl alcohol solution.

In the third step, 7.5 g of polyalkylene oxide diamine (XTJ-501 ^TM , HUNTSMAN) and 107.5 g of isopropyl alcohol were added to a 1 L four-necked flask equipped with a stirrer, an addition funnel and a reflux condenser. After heating and stirring to 80 ° C., 100 g of the branched epoxy polyalkylene oxide-modified polysiloxane 50% isopropyl alcohol solution synthesized in the second step was added, and the reaction was maintained at 80 ° C. for a sufficient time to open all the epoxy. After opening all the epoxy, 251 g of dipropylene glycol was added, and then isopropyl alcohol was removed by distillation under reduced pressure. The remaining amine group was neutralized with acetic acid.

Example 1-1

In Example 1, the prepared product was quaternized with hydrochloric acid 50% of the amine content.

Example 2

In the first step, the same hydrogen side chain polysiloxane as in Example 1 was obtained.

In the second step, the same side chain epoxy polyalkylene oxide modified polysiloxane 50% isopropyl alcohol solution as in Example 1 was obtained.

In the third step, synthesized in the same manner as in Example 1, 0.5g of ethylenediamine and 100g of isopropyl alcohol were added, and after stirring and heating at 80 ° C., 50% of the side chain epoxy polyalkylene oxide-modified polysiloxane synthesized in the second step. After 100 g of isopropyl alcohol solution was added, the reaction was maintained at 80 ° C. for a sufficient time to open all the epoxy. After opening all of the epoxy, 233.3 g of dipropylene glycol was added, followed by distillation under reduced pressure. The remaining amine group was neutralized with acetic acid.

Example 2-1

The prepared product of Example 2 was quaternized 50% of the amine content.

Example 3

In the first step, the same hydrogen side chain polysiloxane as in Example 1 was obtained.

In the second step, 400 g of partially hydrogenated side chain polysiloxane synthesized in the first step was added to a 2 L four-necked flask equipped with a stirrer, an addition funnel and a reflux condenser, and 644 g of isopropyl alcohol and 13.28 g of allylglycidyl ether were added thereto. Give and mix well. 5 ppm of platinum acid was added thereto, followed by heating at 80c for 2 hours, and then 231.38 g of allyl polyalkylene oxide (AAE-550, IC chemical) was added. After confirming the disappearance, the reaction was terminated to obtain a branched epoxy polyalkylene oxide-modified polysiloxane 50% isopropyl alcohol solution.

In the third step, synthesized in the same manner as in Example 1, 1.05 g of ethylenediamine and 105 g of isopropyl alcohol were added thereto, followed by heating and stirring to 80 ° C., and the side chain epoxy polyalkylene oxide-modified polysiloxane 50% synthesized in the second step. After 50 g of isopropyl alcohol solution was reacted at 80 ° C. for 2 hours, 5 g of sock-end epoxy polyalkylene oxide (PG-207P, Kukdo Chemical Co., Ltd.) was added thereto, followed by a holding reaction for 1 hour, and then a side chain epoxy synthesized in the second step. 50 g of a polyalkylene oxide-modified polysiloxane 50% isopropyl alcohol solution was added thereto, and the reaction was maintained at 80 ° C. for 2 hours to fully open the epoxy. After opening all the epoxy, 245 g of dipropylene glycol was added, and then isopropyl alcohol was removed by distillation under reduced pressure. The remaining amine group was neutralized with acetic acid.

Example 3-1

The prepared product of Example 3 was quaternized 50% of the amine content.

Example 4

In the first step, prepare a thermometer, electric stirrer, nitrogen bubbler, condenser and dropping funnel in a 1000 mL round bottom flask. 22.5 g of side chain hydrogen polysiloxane and 658 g of cyclosiloxane were added thereto, 6.9 g of acid clay as an acid catalyst was added thereto, and 10 g of hexamethyldisiloxane was added thereto, and the temperature was raised to 80c to maintain the reaction for 3 hours. After the filter, the mixture was distilled under reduced pressure to 150c to obtain a partial hydrogen side chain polysiloxane having a hydrogen group of 0.5 mmol / g and a viscosity of 200 cP.

In the second step, 400 g of partially hydrogenated side chain polysiloxane synthesized in the first step was added to a 2 L four-necked flask equipped with a stirrer, an addition funnel and a reflux condenser, and 543 g of isopropyl alcohol and 13.28 g of allylglycidyl ether were added thereto. Give and mix well. 5 ppm of platinum acid was added thereto, followed by heating at 80c for 2 hours, and then adding 130.44 g of allyl polyalkylene oxide (AAE-1200, IC chemical). After confirming the disappearance, the reaction was terminated to obtain a branched epoxy polyalkylene oxide-modified polysiloxane 50% isopropyl alcohol solution.

In the third step, synthesized in the same manner as in Example 1, 1.25 g of ethylenediamine and 106 g of isopropyl alcohol were added thereto, followed by heating and stirring to 80 ° C., and the side chain epoxy polyalkylene oxide-modified polysiloxane 50% synthesized in the second step. After adding 50 g of isopropyl alcohol solution and reacting at 80 ° C. for 2 hours, 6 g of sock-end epoxy polyalkylene oxide (PG-207P, Kukdo Chemical Co., Ltd.) was added thereto, followed by a holding reaction for 1 hour. 50 g of a polyalkylene oxide-modified polysiloxane 50% isopropyl alcohol solution was added thereto, and the reaction was maintained at 80 ° C. for 2 hours to fully open the epoxy. After opening all the epoxy, 247 g of dipropylene glycol was added, and then isopropyl alcohol was removed by distillation under reduced pressure. The remaining amine group was neutralized with acetic acid.

Example 4-1

The prepared product of the above example was quaternized to 50% of the amine content.

Table 1 summarizes the basic physical properties of the copolymer and the comparative example for each example.

Viscosity (cPs) Volatile fraction (%) Amine number (%) Example 1 5800 70 0.07 Example 1-1 6900 70 0.04 Example 2 3800 70 0.12 Example 2-1 4500 70 0.6 Example 3 4700 70 0.06 Example 3-1 5600 70 0.03 Example 4 3500 70 0.11 Example 4-1 4500 70 0.05 Comparative example 3800 70 0.10

Comparative example; MPM SRS

Comparative example: MPM (former GE Toshiba) SRS (product name) product received a sample from a textile processing formulator to perform a comparative experiment, has the properties shown in Table 2 below.

Properties Spec. Found Exterior Translucent weak yellow Opaque Weak Yellow Viscosity (cPs) 2500 3800 Amine number (%) 0.13 0.10 Reactant Concentration (%) 30 30 solvent Dipropylene glycol Dipropylene glycol

The test procedure for the fabric softener using the copolymers of Examples and Comparative Examples is as follows.

Test procedure

1) The concentration of the softener in the finishing composition was 0.5-1.0% of the aqueous solution. After the softener tank was installed, the cotton fabric was padded (padding), and the pick-up rate was 70% through the mangle. Treated. The cotton treated with the softening agent was dried in an oven at 180 ° C. for 0.5 minutes, and then measured for flexibility, yellowing, and hygroscopicity.

2) Self-emulsification was measured by increasing the concentration of the softener to 1.0 ~ 10.0%, and the aqueous solution of sodium hydroxide was added to evaluate the gum-up property.

Absorbency rating Flexibility rating Yellowing grade Self emulsifying Gum-up grade Example 1 2 One One One One Example 1-1 One One One One One Example 2 2 One One One Example 2-1 One One One One One Example 3 2 One One One One Example 3-1 One 2 One One One Example 4 2 One One One One Example 3-1 One 2 One One One Comparative example 3 One One One 2

Lower grades mean more flexible, re-inflammatory, yellowing and no gum and gelation.

As shown in Table 3, as a result of the comparison with the silicone fiber softener prepared by the application of the present invention, it can be confirmed that Example 2-1 is excellent or similar to the flexibility and yellowing grade, and excellent hygroscopicity and reinflammability have.

The present invention can be widely used in the chemical industry, the silicone chemical industry, the fabric softener manufacturing industry and the like.

Claims (17)

An amino-modified silicone copolymer according to claim 1, wherein the side chain epoxy polyalkylene oxide-modified silicone compound of Formula 1 and the sock end amino compound of Formula 3 are formed by a copolymerization reaction through an epoxy ring opening reaction with an amine.
[Formula 1]
[R ¹ ₃ Si [(SiO (R ¹ ) ₂ ) _x (SiO (R ¹ R ² (C _a H _2a O) _b H) _y (SiO (R ¹ R ³ X)) _z ] SiR ¹ ₃
(3)
[ZR ⁴ Z]
In the above formula
R ¹ is an alkyl group containing 1 to 4 carbon atoms,
R ² and R ³ are each independently a divalent hydrocarbon group containing 1 to 10 carbon atoms,
R ⁴ is a divalent hydrocarbon group containing 2 to 10 carbon atoms or _a polyalkylene oxide represented by [O (C _a H _2a O) _b ],
X is a divalent organic group formed independently by epoxide ring opening, and is -CH2CH (OH) (CH2) vCH (OH) CH2-, -CH [CH2OH] (CH2) vCH [CH2OH]-, -CH2CH (OH ) (CH2) vCH [CH2OH]-,-(CH2) v-OCH2CH (OH) CH2-,
Where v is 2 to 6,
Z is an amine group any one of primary, secondary and tertiary amines,
a is a positive integer from 2 to 4, b is a positive integer from 1 to 100, x is a positive integer from 1 to 500, y is a positive integer from 1 to 300, z is from 1 to 3 Is a positive integer. The method of claim 1,
The amino-modified silicone copolymer is an amino-modified silicone copolymer, characterized in that the copolymerized by adding the sock end epoxy compound of the formula (2).
(2)
[YO (C _a H _2a O) _b Y]
Y is independently a divalent organic group formed by epoxide ring opening, -CH2CH (OH) (CH2) vCH (OH) CH2-, -CH [CH2OH] (CH2) vCH [CH2OH]-, -CH2CH (OH ) (CH2) vCH [CH2OH]-,-(CH2) v-OCH2CH (OH) CH2-. delete delete The method of claim 2,
X is selected from allyl glycidyl ether group and allyl epoxycyclohexyl group,
Y is a glycidyl ether group, an epoxycyclohexyl alkylene group, w- (3,4) -epoxycyclohexylalkylene, b- (3,4-epoxycyclohexyl) -b-methylethylene, or b- ( An amino modified silicone copolymer, characterized in that it is selected from 3,4-epoxy-4-methylcyclohexyl) -b-methylethylene. delete The method of claim 1,
The amino-modified silicone copolymer characterized in that the amine group connected by the amine group Z is protonated or quaternized. The method of claim 1,
The amino-modified silicone copolymer of Formula 3 is selected from hydrocarbon diamine or polyalkylene oxide diimine. 9. The method of claim 8,
Wherein said hydrocarbon diamine is selected from ethylene diamine, propylene diamine, butylene diamine, hexylene diamine. (A) reacting a side chain hydrogen polysiloxane having an epoxy group and a polyalkylene oxide group at the same time with a cyclosiloxane under a predetermined catalyst to prepare a side chain epoxy polyalkylene oxide-modified polysiloxane of Formula 1 below; And
(B) reacting the side chain epoxy polyalkylene oxide-modified polysiloxane with the sock end amino compound of the following formula (3) under a predetermined solvent, and a copolymerization reaction occurs through an epoxy ring-opening reaction with an amine of the sock end amino compound of the following formula (3) Method for producing an amino-modified silicone copolymer comprising a;
[Formula 1]
[R ¹ ₃ Si [(SiO (R ¹ ) ₂ ) _x (SiO (R ¹ R ² (C _a H _2a O) _b H) _y (SiO (R ¹ R ³ X)) _z ] SiR ¹ ₃
(3)
[ZR ⁴ Z]
In the above formula
R ¹ is an alkyl group containing 1 to 4 carbon atoms,
R ² and R ³ are each independently a divalent hydrocarbon group containing 1 to 10 carbon atoms,
R ⁴ is a divalent hydrocarbon group containing 2 to 10 carbon atoms or _a polyalkylene oxide represented by [O (C _a H _2a O) _b ],
X is a divalent organic group formed independently by epoxide ring opening, and is -CH2CH (OH) (CH2) vCH (OH) CH2-, -CH [CH2OH] (CH2) vCH [CH2OH]-, -CH2CH (OH ) (CH2) vCH [CH2OH]-,-(CH2) v-OCH2CH (OH) CH2-,
Where v is 2 to 6,
Z is an amine group any one of primary, secondary and tertiary amines,
a is a positive integer from 2 to 4, b is a positive integer from 1 to 100, x is a positive integer from 1 to 500, y is a positive integer from 1 to 300, z is from 1 to 3 Is a positive integer. The method of claim 10,
(C) further comprising, after the step (B), adding a polyoxyalkylene composition having a terminal end of the following formula (2).
(2)
[YO (C _a H _2a O) _b Y]
Y is independently a divalent organic group formed by epoxide ring opening, -CH2CH (OH) (CH2) vCH (OH) CH2-, -CH [CH2OH] (CH2) vCH [CH2OH]-, -CH2CH (OH ) (CH2) vCH [CH2OH]-,-(CH2) v-OCH2CH (OH) CH2-. 12. The method of claim 11,
(D) after the step (C), further comprising the step of further adding a side chain epoxy polyalkylene oxide modified polysiloxane of the formula (1); the method of producing an amino-modified silicone copolymer, characterized in that it further comprises. The method of claim 10,
(E) quaternizing the product of step (B); the method of producing an amino-modified silicone copolymer, characterized in that it further comprises. The method of claim 10,
The side chain hydrogen polysiloxane is a partial side chain hydrogen polysiloxane, characterized in that the method for producing an amino-modified silicone copolymer. The method of claim 14,
Wherein the side chain epoxy polyalkylene oxide modified polysiloxane is to pre-react the polyalkylene oxide to the partial hydrogen polysiloxane to ensure the self-emulsification in the silicone compound,
Method (A) is characterized in that the step (B) is carried out after the pre-reaction. The method of claim 10,
The catalyst is a platinum catalyst,
The solvent is a method of producing an amino-modified silicone copolymer, characterized in that any one of alcohol or a mixed solvent of alcohol and water. A fabric softener composition comprising the amino modified silicone copolymer of claim 1.

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