KR20070105429A - Amino oil having goods alkali resistance property - Google Patents

Abstract

An amino-modified silicone copolymer is provided to obtain an excellent fiber softener that has excellent alkali resistance sufficient to prevent oil spots and gum-up during dyeing, improves a fiber touch and shows redyeing capability. A block copolymer comprises alkylene-modified polysiloxane units represented by the formula of [X(CaH2aO)bR1[(SiO(R2)2)cSi(R2)2(CH2)e(SiO(R2)2)c]d Si(R2)2R1(CaH2aO)bX] alternately with polyalkylene oxide units represented by the formula of [YO(CaH2aO)fY]. In the formulae, X represents an opened epoxide; R1 independently represents a divalent hydrocarbyl group; R2 independently represents an alkyl group; Y represents -R4N(R3)(R5)-, wherein R3 is H or alkyl, R4 represents alkylene or cycloalkylene optionally containing a heteroatom, and R5 is alkyl, cycloalkyl or maleate optionally containing a heteroatom; a is a positive integer of 2-4; b is 0 or a positive integer of 1-100; each of c and d independently represents a positive integer of 1-150; f independently represents a positive integer of 1-100; and e is a positive integer of 1-6.

Description

Amino oil having good alkali resistance {Amino oil having goods alkali resistance property}

Fabric softeners are widely used in fibers such as polyester or nylon, and are mainly used in cotton fabrics. Textile processing of common cotton fabrics is a dyeing process for dyeing alkalis and cotton fabrics such as dyes, sodium carbonate (Na ₂ CO ₃ ) or sodium sulfate (Na ₂ SO ₄ ) at a temperature of about 60 to 80 ° C., washing them with water at about 95 ° C. A soaping process, a fabric softener treatment step of impregnating the fabric with a softening emulsion for a predetermined time, and a thermosetting treatment process under high temperature conditions (about 170 ~ 180 ℃). In particular, the soaping process commonly used by processors is a method of passing the fibers through a container containing wash water. In general, however, the water used for washing is not replaced every time, so the alkali component accumulates in the wash water and the alkali component remains in the fiber even after soaping, which causes inspection (oil spots or uneven stains) on the thermoset fiber. do.

Looking at the related art to solve the above problems, US Patent No. 4,242,466 discloses (AB) _n A type siloxane-polyalkylene oxide copolymer, that is, a block copolymer in which siloxane and polyether are alternating Doing.

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

However, silicone amino oils disclosed in the related arts still do not provide satisfactory flexibility and alkali resistance at a practical level, and process instability such as occurrence of crosslinking reactions exists.

The present invention has been made to solve the above problems, the present inventors to form a water-resistant film on the coating site to maintain the effects of the other ingredients added for a long time and to improve the touch (touch) and alkali resistance of the treated fiber In order to introduce an alkylene group which is a hydrophobic group in the silicone main chain, and to prevent gelation by continuous crosslinking reaction of two active hydrogens and an epoxy group present in an amino group during synthesis, an organic compound having an olefin group in an amine is introduced. Was completed.

Accordingly, the technical problem to be solved by the present invention is to provide an amino-modified silicone copolymer having a low crosslinking potential and can be produced by a stable and simple method, and excellent flexibility and reflammability and a fiber softener including the same.

The present invention relates to a block copolymer composed of alternating units of an alkylene-modified polysiloxane of formula (1) and a polyalkylene oxide of formula (2).

[X (C _a H _2a O) _b R ¹ [(SiO (R ² ) ₂ ) _c Si (R ² ) ₂ (CH ₂ ) _e (SiO (R ² ) ₂ ) _c ] _d Si (R ² ) ₂ R ¹ (C _a H _2a O) _b X]

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

In which X represents a ring-opening epoxide;

Each R ¹ independently represents a divalent hydrocarbon group;

Each R ² independently represents an alkyl group;

Y represents -R ⁴ N (R ³ ) (R ⁵ )-;

R ³ here represents hydrogen or an alkyl group;

R ⁴ represents alkylene, or cycloalkylene, which may contain hetero atoms;

R ⁵ represents an alkyl group, cycloalkyl group or malate, which may contain hetero atoms;

a is a positive integer from 2 to 4; b is 0 or a positive integer from 1 to 100; c and d are each independently a positive integer from 1 to 150; f is a positive integer from 1 to 100; e represents a positive integer of 1 to 6;

Wherein the ring-opening epoxide X may contain an aliphatic, cycloaliphatic or aromatic ring. They may also contain hydroxy groups or ether bonds, preferably -CH ₂ CH (OH) (CH ₂ ) _v CH (OH) CH _2- , -CH [CH ₂ OH] (CH ₂ ) _v CH [CH ₂ OH]-, -CH ₂ CH (OH) (CH ₂ ) _v CH [CH ₂ OH]-,-(CH ₂ ) _v -OCH ₂ CH (OH) CH _2- , or-(CH ₂ ) _v OCH ₂ CH (CH ₂ [OH])-(v represents a positive integer of 2 to 6), wherein the ring-opening epoxide is an epoxycyclohexyl alkylene group, ω- (3,4-epoxycyclohexyl) Alkylene, β- (3,4-epoxycyclohexyl) ethylene, β- (3,4-epoxycyclohexyl) -β-methylethylene, or β- (3,4-epoxy-4-methylcyclohexyl)- can be derived from β-methylethylene.

In the general formula 1 R ¹ represents a divalent hydrocarbon group, preferably a substituted or may optionally contain an ether bond by a hydroxy group and preferably containing from burnt wish of 10 or less, than a C _{1 -4-alkylene} desirable.

In addition, R ² represents an alkyl group, preferably C _{1 -4} alkyl group, and more preferably methyl.

Y in Formula 2 is an amine represented by -R ⁴ N (R ³ ) (R ⁵ )-; Wherein R ³ is a hydrogen or an alkyl group, preferably hydrogen or alkyl C _{1 -4,} and more preferably represents a hydrogen or methyl. R ⁴ is an alkylene or cycloalkyl which may contain a hetero atom alkylene, preferably an oxygen, sulfur, or which may contain a hetero atom selected from nitrogen _-4 C ₂ alkylene or C _{3 -10} cycloalkylene More preferably ethylene or propylene. R ⁵ represents an alkyl group, a cycloalkyl group or a maleate which may contain a hetero atom, more preferably methyl, ethyl or malate.

A in the general formulas (1) and (2) is an integer of 2 to 4, preferably 2 or 3; b is 0 or a positive integer from 1 to 100, preferably 0; c and d are each independently a positive integer of 1 to 150, preferably 50 to 100; f is a positive integer from 1 to 100, preferably from 10 to 50; e represents a positive integer of 1 to 6, preferably 2 to 4.

When a is less than 2 and exceeds 4, it is difficult to self-emulsify. When b and f are each greater than 100, the storage stability of the copolymer is poor, and when f is 0, it is not self-emulsified. In addition, when c and d are less than 1, physical properties such as flexibility during fiber processing may be reduced. When the c and d are greater than 150, the viscosity may be greatly increased, leading to difficulty in manufacturing, and when e is 0, desired alkali resistance may be obtained. It is not possible, and if it exceeds 6, it is difficult to manufacture.

In particular the copolymers according to the invention show that R ² represents a methyl group, R ³ represents hydrogen, R ⁴ represents propylene: R ⁵ represents maleate and a is 2 or 3; b is 0; c and d are positive integers from 50 to 150; f is a positive integer from 10 to 50; It is preferable that e is a positive integer of 2-4, More preferably, it contains the structure of following formula (3).

HN (R ⁵ ) CH (Me) CH ₂ O (C _a H _2a O) _f CH ₂ (Me) CHN (R ⁵ ) [CH ₂ CH (OH) CH ₂ O (CH ₂ ) ₃ [(SiO (Me ) ₂ ) _c Si (Me) ₂ CH ₂ CH ₂ (SiO (Me) ₂ ) _c ] _d Si (Me) ₂ (CH ₂ ) ₃ OCH ₂ —CH (OH) CH ₂ —N (R ⁵ ) CH ( Me) CH ₂ O (C _a H _2a O) _f CH ₂ CH (Me) N (R ⁵ )] _y H

In the above formula, Me represents methyl, R ⁵ represents maleate, and y represents a positive integer of 2 to 1000 depending on the values of b + f and c + d of the general formula (1).

The copolymer according to the invention is preferably a copolymer of type (AB) _n A _wherein A represents a polyalkylene oxide unit of formula (2), B represents an alkylene modified polysiloxane unit of formula (1), where n is 2 It is a positive integer from to 1,000. The total number of repeat units is limited only by aspects of the operability of the high viscosity material, which increases in viscosity as the number of units increases, but in practice there must be at least two units.

The molecular weight of the copolymers according to the invention can be changed by adjusting the molar ratio of epoxy component to amino component and by changing the number of siloxy groups and the number of oxyalkylene units in the polysiloxane block. Another important factor controlling the properties of the copolymers according to the invention is also the relative content of silicon in the molecule, i.e. the c + d and b + f values. Copolymers with higher silicon content are usually more hydrophobic and therefore less soluble in water and give higher flexibility.

The copolymer according to the present invention introduces a hydrophobic alkylene group into the silicone backbone to form a water-resistant film on the coating site for long-term effects of the added components and to improve the touch and alkali resistance of the treated fiber. In order to prevent gelation by the continuous crosslinking reaction of two active hydrogens present in the amino group and the epoxy group during the synthesis, a maleate-substituted amino polyalkylene oxide is introduced to reduce the possibility of crosslinking. It is excellent in reflammability.

The present invention also relates to an emulsion-like fibrous softener comprising a copolymer and water.

The emulsion of the copolymer of the present invention (fiber softener) has the advantage of being easily diluted (self-emulsifying) by simply adding a small amount of emulsifier without going through an emulsification process. Unlike general amino modified silicone in which amino group is added to the side chain of molecule, it is added in linear form so that the spacing of amino groups is constant and the surface area is added to fiber. It maintains the characteristics (flexibility) and exhibits a dry softness that gives a soft voluptuous feeling inside the fiber.

The present invention also relates to a textile product treated with the fabric softener. The fabric softeners according to the present invention can be applied to various textile products according to methods commonly used for treating fibers, hair or textiles such as spraying, impregnation or kiss rolls. Textile products that can be treated with the fabric softeners of the present invention include natural fibers such as hair, cotton, silk, flax, cellulose, paper (including tissue paper) and wool; Synthetic fibers such as polyester, polyamide, polyacrylonitrile, polyethylene, polypropylene and polyurethane; Inorganic fibers such as glass fiber or carbon fiber; And fabrics made from mixtures thereof.

In general, the copolymer according to the present invention may be treated in an amount of 5% or less, preferably 0.25 to 2.5% by weight of the fiber product, and according to other applications, surfactants, curable resins, preservatives, dyes, Conventional additives commonly used in hair or textile products, such as colorants, composition aids, can be used together.

The present invention also provides a method for preparing a compound of formula 6 by reacting a dialkylpolysiloxane of formula 4 with a hydrogen terminal diorganosiloxane of formula 5 in the presence of a hydrosilylation catalyst;

A second step of preparing an epoxy-terminated alkylene-modified polysiloxane of formula (I) by reacting the compound of formula (6) obtained in the first step with an epoxide containing an alkylene group (X (C _a H _2a O) _b R ^1- ) step;

A third step of reacting a polyalkylene oxide terminated with an amino group of formula (2) with an alkylene modified polysiloxane of formula (1) obtained in a second step

It relates to a method for producing a block copolymer composed of alternating units of an alkylene-modified polysiloxane of formula (1) and a polyalkylene oxide of formula (2) comprising a.

CH ₂ = CH (CH ₂ ) _g (SiO (R ² ) ₂ ) _c Si (R ² ) ₂ (CH ₂ ) _g CH = CH ₂

H (SiO (R ² ) ₂ ) _c Si (R ² ) ₂ H

H [(SiO (R ² ) ₂ ) _c Si (R ² ) ₂ (CH ₂ ) _e (SiO (R ² ) ₂ ) _c ] _d Si (R ² ) ₂ H

[Formula 1]

[X (C _a H _2a O) _b R ¹ [(SiO (R ² ) ₂ ) _c Si (R ² ) ₂ (CH ₂ ) _e (SiO (R ² ) ₂ ) _c ] _d Si (R ² ) ₂ R ¹ (C _a H _2a O) _b X]

[Formula 2]

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

In the above formula

X represents a ring-opening epoxide;

Each R ¹ independently represents a divalent hydrocarbon group;

Each R ² independently represents an alkyl group;

Y represents -R ⁴ N (R ³ ) (R ⁵ )-;

R ³ here represents hydrogen or an alkyl group;

R ⁴ represents alkylene, cycloalkylene, which may contain heteroatoms;

R ⁵ represents an alkyl group, cycloalkyl group, or maleate which may contain heteroatoms;

a is a positive integer from 2 to 4; b is 0 or a positive integer from 1 to 100; c and d are each independently a positive integer from 1 to 150; f is each independently a positive integer of 1 to 100; e is a positive integer of 1 to 6; g represents a positive integer of 1 to 6.

The reaction is carried out in a suitable solvent such as alcohol or a mixture of alcohol and water. Generally epoxy endblocked alkylene modified polysiloxanes are added to the amine solution in the reaction solvent. After the reaction, the copolymer solution can be neutralized with acetic acid and the solvent exchanged with non-flammable solvents such as water, propylene glycol, and dipropylene glycol. The reaction product can be separated by distillation of the solvent under atmospheric pressure or reduced pressure, and the separated reaction product can be a viscous oil or wax depending on the molecular weight and ethylene oxide content of the copolymer.

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

Example 1

In the first step, 21 g of hydrogen-terminated dimethylsiloxane and 380 g of divinylpolysiloxane were stirred at room temperature. After adding chloroplatinic acid (5 to 100 ppm as Pt), the reaction was maintained at 60 ° C. until no vinyl group was detected, thereby obtaining a dihydrogen alkylene-modified polysiloxane represented by the following formula (7).

HMe ₂ Si-O [(SiO (Me) ₂ ) _c Si (Me) ₂ CH ₂ CH ₂ (SiO (Me) ₂ ) _c ] _d Si (Me) ₂ H

Wherein Me represents methyl and c and d are an integer from 50 to 150.

In a second step, 390 g of the dihydrogen alkylene modified polymer of Formula 7 were heated to 80 ° C. in a 1 L four neck flask. After adding chloroplatinic acid (5 to 100 ppm as Pt), 15.5 g of allylglycidyl ether was slowly added at 80 ° C. The temperature was maintained at 80-90 ° C. until no reacted Si-H was detected in the analysis. Excess allyl glycidyl ether was removed by vacuum distillation at 50 mmHg and 120 ° C. to give a diepoxy alkylene modified polymer of the formula (8).

CH ₂ CH (O) CH ₂ O (CH ₂ ) ₃ Me ₂ Si-O [(SiO (Me) ₂ ) _c Si (Me) ₂ CH ₂ CH ₂ (SiO (Me) ₂ ) _c ] _d Si (Me ) _2- (CH ₂ ) ₃ OCH ₂ (O) CHCH ₂

In the third step, 31.5 g of aminopolyalkylene oxide and 1 g of dimethylmaleate were reacted at 45 ° to prepare a maleate substituted amino polyalkylene oxide of the following Chemical Formula 9.

(CH ₃ COO) CH _2- (CH ₃ COO) CH-NH-CH (CH ₃ ) CH ₂ O (C _a H _2a O) _f CH ₂ CH (CH ₃ ) -NH-CH (CH ₃ COO)- CH ₂ (COOCH ₃ )

28 g of the compound of formula 9 and 157 g of 2-propanol were added to a 1 L four-necked flask equipped with a stirrer, a dropping funnel, a reflux condenser and a thermometer. The reaction temperature was adjusted to 80 ° C., 100 g of the compound of Formula 8 was added dropwise for 1 to 2 hours through a dropping funnel, and after confirming that all the epoxy functional groups were consumed, acid neutralization was performed. After adding 220 g of dipropylene glycol, 2-propanol was distilled off to obtain a silicone backbone alkylene-modified dimethylmaleate amino polymer.

Example 2

Except for reacting 31 g of the compound of Formula 9 and 100 g of the compound of Formula 8 in the third step of Example 1 was prepared in the same manner as in Example 1 to obtain a silicone backbone alkylene modified dimethylmaleate amino polymer.

Comparative example

In the first step, the reaction of tetramethyldisiloxane (1.5 g) and dimethylcyclic siloxane (100 g) was maintained for 6 hours under a temperature of 60 ° C. and a sulfuric acid catalyst. After the acid catalyst was removed, the unreacted dimethylcyclic siloxane was distilled at 150 ° C. to obtain a dihydrogen siloxane of the following Chemical Formula 10.

H (SiO (Me) ₂ ) _c Si (Me) ₂ H

In the above formula, Me represents a methyl group and c is a positive integer of 50 to 150.

In a second step, 390 g of hydrogen end dimethylsiloxane (Formula 12) were heated to 80 ° C. in a 1 L four neck flask. After adding chloroplatinic acid (5 to 100 ppm as Pt), 15.5 g of allylglycidyl ether was slowly added at 80 ° C. The temperature was maintained at 80-90 ° C. until no reacted Si-H was detected in the analysis. Excess allyl glycidyl ether was removed by vacuum distillation at 50 mmHg and 120 ° C. to give diepoxysiloxane of formula (11).

CH ₂ CH (O) CH ₂ O (CH ₂ ) ₃ Me ₂ Si-O (SiO (Me) ₂ ) _c Si (Me) ₂ (CH ₂ ) ₃ OCH ₂ (O) CHCH ₂

In the third step, 31 g of amino polyalkylene oxide and 157 g of 2-propanol were added into a 1 L four-necked flask equipped with a stirrer, dropping funnel, reflux condenser and thermometer. The reaction temperature was adjusted to 80 ° C., 100 g of diepoxysiloxane (Formula 11) was added dropwise for 1 to 2 hours through a dropping funnel, and the acid was neutralized after confirming that all epoxy functional groups were consumed. After adding 220 g of dipropylene glycol, 2-propanol was distilled off to obtain a silicone amino polymer.

Table 1 summarizes the basic physical properties of the copolymers prepared in Examples and Comparative Examples.

(A) Silicone backbone alkylene modified dimethylmaleate amino polymer

(B) silicone backbone alkylene modified dimethylmaleate amino polymer,

(C) amino polymer

Experimental Example: (AB) Softness characteristics test of _n A copolymer

The fabric softener using the copolymers prepared in Examples and Comparative Examples was applied to the cotton. The concentration of the softener in the finishing composition was such that the effective concentration of the fiber was 1%. The softener was impregnated with cotton and then wrapped in a mangled thickness. The surface coated with the softening agent to a certain thickness is cured in an oven at 170 ° C. for 3 minutes. Flexibility and yellowing data are summarized in Table 2 below.

* Alkali resistance test (stable test of emulsion emulsion): 20 g / L of sodium carbonate was added to the copolymer 1% emulsifier, and then put into the 80 ° C. mixing oven for 10 minutes, and then the precipitate precipitate was filtered by paper filter and filtered. Was determined to obtain a percentage.

As shown in Table 2, compared with the silicone fiber softener prepared by the application of the present invention, the fabric softener (B) prepared in Example 2 was prepared by Comparative Example under the condition that the alkali concentration was 20 g / L. It can be seen that the fiber softener (C) has more than twice the effect on alkali resistance and also excellent in flexibility and reinflammability.

As described above, the alkyl modified silicone amino polymer according to the present invention is excellent in alkali resistance to prevent oil spots and inspection during the dyeing process, excellent touch (touch) and re-inflammation is possible. In addition, cross-linking can be prevented in advance when the fabric softener is synthesized, which is advantageous in manufacturing.

Claims (7)

A block copolymer composed of alternating units of an alkylene-modified polysiloxane of Formula 1 and a polyalkylene oxide of Formula 2. [Formula 1] [X (C _a H _2a O) _b R ¹ [(SiO (R ² ) ₂ ) _c Si (R ² ) ₂ (CH ₂ ) _e (SiO (R ² ) ₂ ) _c ] _d Si (R ² ) ₂ R ¹ (C _a H _2a O) _b X] [Formula 2] [YO (C _a H _2a O) _f Y] In the above formula X represents a ring-opening epoxide; Each R ¹ independently represents a divalent hydrocarbon group; Each R ² independently represents an alkyl group; Y represents -R ⁴ N (R ³ ) (R ⁵ )-; R ³ here represents hydrogen or an alkyl group; R ⁴ represents alkylene, cycloalkylene, which may contain heteroatoms; R ⁵ represents an alkyl group, cycloalkyl group, or maleate which may contain heteroatoms; a is a positive integer from 2 to 4; b is 0 or a positive integer from 1 to 100; c and d are each independently a positive integer from 1 to 150; f is each independently a positive integer of 1 to 100; e represents a positive integer of 1 to 6; The ring-opening epoxide X of claim 1, wherein the ring-opening epoxide X is -CH ₂ CH (OH) (CH ₂ ) _v CH (OH) CH _2- , -CH [CH ₂ OH] (CH ₂ ) _v CH [CH ₂ OH] , -CH ₂ CH (OH) (CH ₂ ) _v CH [CH ₂ OH]-,-(CH ₂ ) _v -OCH ₂ CH (OH) CH _2- , or-(CH ₂ ) _v OCH ₂ CH (CH ₂ [OH])-(v represents a positive integer from 2 to 6). The compound of claim 1, wherein R ² represents a methyl group, R ³ represents hydrogen, R ⁴ represents propylene, R ⁵ represents maleate, and a is 2 or 3; b is 0; c and d are positive integers from 50 to 150; f is a positive integer from 10 to 50; e is a copolymer of positive integer of 2 to 4. The copolymer according to claim 1, comprising a structure represented by the following formula (3). [Formula 3] HN (R ⁵ ) CH (Me) CH ₂ O (C _a H _2a O) _f CH ₂ (Me) CHN (R ⁵ ) [CH ₂ CH (OH) CH ₂ O (CH ₂ ) ₃ [(SiO (Me ) ₂ ) _c Si (Me) ₂ CH ₂ CH ₂ (SiO (Me) ₂ ) _c ] _d Si (Me) ₂ (CH ₂ ) ₃ OCH ₂ —CH (OH) CH ₂ —N (R ⁵ ) CH ( Me) CH ₂ O (C _a H _2a O) _f CH ₂ CH (Me) N (R ⁵ )] _y H Wherein Me is methyl, R ⁵ is maleate, a, f, c and d are as defined in claim 1 and y is a positive integer from 2 to 1,000. Fibrous softener in emulsion comprising copolymer of claim 1 Textile product treated with the fabric softener according to claim 5. A first step of preparing a compound of Chemical Formula 6 by reacting a dialkenylpolysiloxane of Chemical Formula 4 with a hydrogen terminal diorganosiloxane of Chemical Formula 5 in the presence of a hydrosilylation catalyst; A second step of preparing an epoxy-terminated alkylene-modified polysiloxane of formula (I) by reacting the compound of formula (6) obtained in the first step with an epoxide containing an alkylene group (X (C _a H _2a O) _b R ^1- ) step; And A third step of reacting a polyalkylene oxide terminated with an amino group of formula (2) with an alkylene modified polysiloxane of formula (1) obtained in a second step Method for producing a block copolymer composed of alternating units of the alkylene-modified polysiloxane of formula (1) and the polyalkylene oxide of formula (2) comprising a [Formula 4] CH ₂ = CH (CH ₂ ) _g (SiO (R ² ) ₂ ) _c Si (R ² ) ₂ (CH ₂ ) _g CH = CH ₂ [Formula 5] H (SiO (R ² ) ₂ ) _c Si (R ² ) ₂ H [Formula 6] H [(SiO (R ² ) ₂ ) _c Si (R ² ) ₂ (CH ₂ ) _e (SiO (R ² ) ₂ ) _c ] _d Si (R ² ) ₂ H [Formula 1] [X (C _a H _2a O) _b R ¹ [(SiO (R ² ) ₂ ) _c Si (R ² ) ₂ (CH ₂ ) _e (SiO (R ² ) ₂ ) _c ] _d Si (R ² ) ₂ R ¹ (C _a H _2a O) _b X] [Formula 2] [YO (C _a H _2a O) _f Y] In the above formula X represents a ring-opening epoxide; Each R ¹ independently represents a divalent hydrocarbon group; Each R ² independently represents an alkyl group; Y represents -R ⁴ N (R ³ ) (R ⁵ )-; R ³ here represents hydrogen or an alkyl group; R ⁴ represents alkylene, cycloalkylene, which may contain heteroatoms; R ⁵ represents an alkyl group, cycloalkyl group, or maleate which may contain heteroatoms; a is a positive integer from 2 to 4; b is 0 or a positive integer from 1 to 100; c and d are each independently a positive integer from 1 to 150; f is each independently a positive integer of 1 to 100; e is a positive integer from 1 to 6; g represents a positive integer of 1-6.