JP2003525969A - Method for producing sulfonated polyester compound - Google Patents

Abstract

  (57) [Summary] The sulfonated acid or ester is reacted with a hydroxy-containing compound to form a sulfonated hydroxy-terminated ester, which in turn undergoes transesterification with a poly (ethylene terephthalate) -based polyester, followed by polymerization. A method for producing a sulfonated polyester compound suitable for use as an antifouling agent and / or a fiber sizing agent, which undergoes a condensation reaction to form a desired sulfonated polyester compound.

Description

Detailed Description of the Invention

Related Application This application is a US provisional patent application No. 60/16 filed December 1, 1999.
It claims priority of No. 8,240.

[0002] The present invention, a sulfonated acid or ester is reacted with a hydroxy-containing compound to form a sulfonated hydroxy terminated groups with ester, the ester is then poly (ethylene) terephthalate-based polyester As a soil releasing agent and / or a textile sizing agent, which undergoes a transesterification reaction with a subsequent polycondensation reaction to form the desired sulfonated polyester compound. It relates to a method for producing a sulfonated polyester compound suitable for use. The present invention provides lower costs, shorter cycle times and improved yields over conventional methods of making sulfonated polyester compounds.

BACKGROUND filaments of the invention, fibers, fabric, sulfonated polyester compounds for removing dirt and stains from a wide variety of substrates including films, etc. are known. Low molecular weight sulfonated polyester compounds have typically been used as antifouling agents in laundry detergents, while higher molecular weight sulfonated polyester compounds have been used for sizing fibers.

US Pat. No. 3,962,152 discloses a detergent composition containing a polymer obtained by reacting dimethyl terephthalate with polyethylene glycol as an antifouling agent.

US Pat. Nos. 4,863,619, 4,925,577 and 5,
041,230 generally discloses methods for improving the processability of antifouling polymers.

US Pat. No. 4,999,128 describes poly (ethylene terephthalate /
Copolymers of ethylene isophthalate) and related copolymers made by reacting the ester with polyethylene glycol.

US Pat. No. 5,142,020 describes antifouling accelerators and cleaning agents obtained by polymerizing monomers such as dicarboxylic acids / esters / anhydrides, dihydric alcohols and polyethylene glycols. Is disclosed.

Sulfonated polyester compounds have received much attention as effective antifouling agents. For example, U.S. Pat. No. 3,557,039 discloses water and a water insoluble crystallizable block or graph polymeric compound.
And discloses a stable aqueous dispersion containing such a polymeric compound containing linear polyethylene terephthalate segments having sufficient ethylene terephthalate units to impart crystallinity to the compound. These polymers are made by reacting monomers containing sodium dimethylsulfoisophthalate.

US Pat. No. 4,427,557 discloses sulfonated copolymers used to prepare anionic fiber treating compositions in which the polymerizable monomer comprises dimethylsulfoisophthalate. ing.

US Pat. No. 4,702,857 describes monomers such as dimethyl terephthalate, dimethyl sulfoisophthalate, polyethylene glycol and polyethylene glycol monoethers used as antifouling agents in detergent formulations. A sulfonated copolymer obtained by polymerizing is disclosed.

US Pat. No. 5,599,782 also discloses sulfonated polyester compounds useful as antifouling agents. The polymerizable monomers listed in this document,
There are m-sodiosufobenzoic acid, dimethylsodiosulfoisophthalate, dimethylterephthalate, terephthalic acid and ethylene glycol.

US Pat. No. 5,728,671 discloses sulfonated polyester compounds useful as antifouling agents with whitening properties. U.S. Pat. No. 5,786,318 discloses polymerizing monomers such as sulfonated aromatic dicarboxylic acids to produce antifouling polymers for detergent compositions. Other antifouling polymers, including sulfonated polymers, are described in US Pat.
89, 365, 5,789,366 and 5,789,367.

A polyester compound for use as an antifouling agent and / or a fiber sizing agent,
In particular, the market for sulfonated polyester compounds for this purpose has grown significantly in recent years. However, the increasing demand has stimulated efforts to improve the production capacity of the desired sulfonated polyester compounds.

Conventional processes for producing sulfonated polyester compounds for use as antifouling agents and / or fiber sizing agents include expensive starting materials, process cycles (ie, initial It may take a long time (from the reaction to the production of the finished product) and / or a low yield of the desired product or a low relative reactor throughput for various reasons. There's a problem. As an example, the transesterification reaction of dimethyl terephthalic acid and dimethyl-5-sulfoisophthalate with an excess of ethylene glycol, followed by the esterification reaction with terephthalic acid, and then the polycondensation reaction to produce a sulfonated polyester compound is carried out in a 15-ton batch A typical cycle time of about 38.5 hours is required to process the above polyesters. Because this reaction produces 35% distillate, its long cycle times and low yields or reactor throughputs make it very difficult to meet the growing market demand for such sulfonated polyester compounds. Making it difficult.

SUMMARY OF THE INVENTION The present invention relates to a process for the preparation of sulfonated polyester compounds wherein the reaction yields and cycle times are significantly improved over conventional processes for preparing the same or similar compounds. The process of the present invention generally involves reacting a sulfonated acid or the corresponding alkyl ester with a hydroxy containing compound to produce a sulfonated ester intermediate compound, which intermediate compound is then reacted to the desired molecular weight. To produce a sulfonated polyester compound suitable for use as an antifouling agent and / or a fiber sizing agent, which is reacted with a polyester selected to give a final polyester compound having

In one particular aspect of the present invention there is provided a process for preparing a sulfonated polyester compound suitable for use as an antifouling agent and / or a fiber sizing agent: a) Formula (I)

[0017]

[Chemical 5] Wherein X is a cation, R is an aryl group, Y is selected from the group consisting of hydrogen and alkyl groups, and n is a positive integer. (II)

[0018]

[Chemical 6] Wherein R ₁ is selected from the group consisting of an alkyl group which may be substituted with an alkyl group or an aryl group, a cycloalkyl group and an aryl group, and m is a positive integer. Compounds, and optionally Formula (III)

[0019]

[Chemical 7] Wherein R ₂ is selected from the group consisting of alkyl and aryl groups, Z is selected from the group consisting of hydrogen and alkyl groups, and p is a positive integer. Formula (IV)

[0020]

[Chemical 8] (Wherein R ₃ and R ₄ are each independently selected from the group consisting of hydrogen and alkyl groups, and q is a positive integer.) And at least one ester compound intermediate There is provided a process as described above, comprising the steps of forming a body and reacting the resulting ester compound intermediate with a homo- or co-poly (ethylene terephthalate) to form a sulfonated polyester.

[0021] for use as a detailed description antifouling agent and / or fiber sizing agent of the invention, a method of producing a sulfonated polyester compounds according to the invention, formula (I)

[0022]

[Chemical 9] (Wherein X is a cation, R is an aryl group optionally substituted with an alkyl group or an aryl group, Y is selected from the group consisting of hydrogen and an alkyl group, and n is a positive integer. The reaction of at least one compound having Cations available for X include, for example, sodium, lithium, potassium, NH ₄ and tetrabutylphosphonium. Sodium is the preferred cation for compounds of formula (I). R is an aryl group such as phenyl and naphthyl.

The starting sulfonated compound may be in the acid form where Y is hydrogen, or in the form of an alkyl ester. Preferred alkyl groups are methyl, ethyl, propyl and butyl, with methyl being the preferred alkyl group. The number of acid groups or ester groups is 1 to 4, preferably 1 or 2. The most preferred number of acid groups or ester groups is two.

Examples of suitable compounds of formula (I) include dimethyl-5-sodiosulfoterephthalate, 5-sodiosulfoterephthalic acid, 5-lithoisophthalic acid, 3-sodiosulfobenzoic acid and 4 -Sodiosulfodiphenyl-4,4
There is'-dicarboxylic acid. Preferred compounds of formula (I) are sodiosulfoisophthalic acid and 3-sodiosulfobenzoic acid.

A compound of formula (I) is reacted with a hydroxy containing compound of formula (II) .R _1- (OH) m. The hydroxy containing compound is selected from the group consisting of monools, diols and polyols. R ₁ is selected from the group consisting of unsubstituted alkyl, cycloalkyl and aryl groups, which groups may be substituted with alkyl and aryl groups. Preferred alkyl groups are those having 1-8 carbon atoms, with methyl, ethyl, propyl and butyl being most preferred. Preferred cycloalkyl groups are those having 5-8 carbon atoms such as cyclohexanyl. Preferred aryl groups for R ₁ are phenyl and naphthyl. m is preferably in the range of 1 to 4, and 2 is most preferable. Preferred compounds of formula (II) are ethylene glycol, 1,2-propylene glycol, 1,
3-propanediol, neopentyl glycol, glycerol, 1,2-butylene glycol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol and 1,4-cyclohexane. There is dimethanol.

Besides the compounds of the formulas (I) and (II), the reaction depends on the use of the final polymer, the reaction of the formula (III)

[0027]

[Chemical 10] Can also be performed in the presence of. R ₂ is selected from the group consisting of an alkyl group and an aryl group, and these groups may be substituted with an alkyl group or an aryl group. Z is selected from the group consisting of hydrogen and alkyl groups, and p is a positive integer. Preferred alkyl groups are those having 1-12 carbon atoms. Preferred alkyl groups for Z are those having 1 to 4 carbon atoms. The preferred values of p are 1 and 2. Typical compounds when R ₂ is an alkyl group include adipic acid, succinic acid, sebacic acid, azelaic acid, glutaric acid and suberic acid, and their corresponding alkyl esters. Typical compounds in which R ₂ is an aryl group include terephthalic acid, isophthalic acid, orthophthalic acid, 1,
2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid, 1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3- There are naphthalenedicarboxylic acids, 2,6-naphthalenedicarboxylic acids, 2,7-naphthalenedicarboxylic acids and their corresponding alkyl esters.

[0028]   Formula (IV):

[0029]

[Chemical 11] Where R ₃ and R ₄ are each independently selected from the group consisting of hydrogen and alkyl groups, and q is a positive integer. Are used as optional starting materials. You can also

Preferred alkyl groups for R ₃ are those having 1 to 4 carbon atoms. Preferred alkyl groups for R ₄ are those having 1 to 12 carbon atoms, especially methyl and lauryl. The preferable value of q is 2 to 20. The optional expression (I
Typical compounds having V) include polyethylene glycol, polypropylene glycol, and block copolymers of polyethylene glycol and polypropylene glycol, and their corresponding alkyl monoethers. The compound of formula (IV) preferably has a molecular weight of about 1,000 or less.

Compounds of formula (I) and (II), optionally of formulas (III) and (IV
The reaction in the presence of at least one compound of) is typically about 12
It is carried out at a temperature of 0 to 280 ° C, preferably about 130 to 190 ° C. This reaction is
Typically, for example, titanium (IV) (triethanolaminato) isopropoxide, titanium (IV) propoxide, titanium (IV) butoxide, manganese acetate,
It is carried out in the presence of a catalyst capable of catalyzing esterification and / or transesterification reactions, such as antimony trioxide, hydrated monobutyltin oxide and magnesium oxide. Other suitable catalysts will be familiar to those skilled in the art. The preferred catalyst is titanium (IV) (triethanolaminato) isopropoxide.

Compounds of formula (I) and (II), and optionally of formula (III
And the reaction of at least one compound of (IV) produces at least one ester compound intermediate. This ester compound intermediate is then continuously or intermittently reacted with homo- or co-poly (ethylene terephthalate) to produce the desired sulfonated polyester compound. The reaction is typically carried out at a temperature of about 150-280 ° C, preferably about 180-260 ° C. After all of the above poly (ethylene terephthalate) has melted, a vacuum of about 600-0.5 mmHg can be applied, depending on the desired molecular weight.

A preferred poly (ethylene terephthalate) compound for reacting with the above ester compound intermediate is polyethylene terephthalate and a comonomer selected from the group consisting of isophthalate, diethylene glycol, propylene glycol and 1,4-cyclohexanedimethanol. It is a copolymer. The resulting reaction produces a sulfonated polyester compound, where the position and number of sulfonated groups is determined by the proper choice of starting materials. Formula (I) when n is 1
By selecting the compound of at least some of the sulfonated groups appear as end groups in the polyester chain. By using at least one compound of formula (I) where n is greater than 1, at least some of the sulfonated groups appear intermittently in the polyester compound and not as terminal groups.

The following examples are illustrative of aspects of the present invention and are not intended to limit the invention, which is encompassed by the claims that form a part of this application. Examples Example 1: 350 g ethylene glycol, 200 g 5-sodiosulfoisophthalic acid, 20 g isophthalic acid and 1 in a 1 liter polymerization reactor equipped with mechanical stirrer, packed reflux column, nitrogen inlet and heat source. 0.2 g of titanium (IV) (triethanolaminato) isopropoxide was added. The mixture was heated to 230 ° C and held at that temperature for 30 minutes. 380 g of poly (ethylene terephthalate) was added and the mixture was heated to 230 ° C. An additional 440 g of poly (ethylene terephthalate) was added and the mixture was heated to 260 ° C. When the temperature of the batch reached 260 ° C, vacuum was applied to 200 mmHg and the polymer was held for 20 minutes then cooled to 160 ° C for discharge. The resulting polymer exhibited excellent antifouling properties. Example 2: The method and material described in Example 1 was repeated, except that a mixture of 250 g diethylene glycol and 50 g ethylene glycol was used as the starting material instead of 350 g ethylene glycol. The resulting polymer exhibited excellent antifouling properties. Example 3: The method and materials described in Example 1 were repeated except that 5-lysosulfoisophthalic acid was used instead of 5-sodiosulfoisophthalic acid. The resulting polymer exhibited excellent antifouling properties. Example 4: The method and material described in Example 1 was repeated, except that the starting material was heated to 185 ° C and held for 30 minutes before adding polyethylene terephthalate. Example 5: A mixture of 201 g of 5-sodiosulfoisophthalic acid, 300 g of ethylene glycol and 150 g of polyethylene glycol having a molecular weight of 200 is prepared as 185
Heat to ° C and hold for 30 minutes. To this mixture was added 380 g of a 60:40 weight ratio copolymer of poly (ethylene terephthalate-ethylene isophthalate) and the resulting mixture was heated to 235 ° C. Then add 4 to this mixture.
40 g of the same copolymer were added and heated at 250 ° C. under atmospheric pressure for 2 hours, followed by cooling to 160 ° C. for discharge. The resulting polymer exhibited excellent antifouling properties. Example 6: 140 g propylene glycol, 350 g ethylene glycol, 175 g
A mixture of 3-sodiosulfobenzoic acid and 210 g of 5-sodioisophthalic acid was heated to 230 ° C and held for 30 minutes. To this mixture was added 380 g of poly (ethylene terephthalate) and then heated to 230 ° C. Then 440 g of the same copolymer was added to this mixture and heated at 250 ° C. under atmospheric pressure for 2 hours, followed by cooling to 160 ° C. for discharge. The resulting polymer exhibited excellent antifouling properties. Example 7: 140 g propylene glycol, 350 g ethylene glycol, 175 g
A mixture of 3-sodiosulfobenzoic acid and 210 g of 5-sodioisophthalic acid was heated to 230 ° C and held for 30 minutes. To this mixture was added 380 g of poly (ethylene terephthalate) and then heated to 230 ° C. Thereafter, an additional 440 g of poly (ethylene terephthalate) was added and the mixture was added to 2
Heated to 50 ° C. When the temperature reached 250 ° C., vacuum was applied and the batch was held at 5 mm Hg for 5 hours and then discharged. The resulting polymer exhibited excellent fiber sizing properties. Example 8: 450 g ethylene glycol, 160 g isophthalic acid, 171 g 5-sodiosulfoisophthalic acid, 0.08 g antimony trioxide and 0.6 g titanium propoxide are combined and heated to 230 ° C., 30 Hold for minutes. To this mixture was added 360 g poly (ethylene terephthalate) and this was heated to 240 ° C. Thereafter, a further 380 g of poly (ethylene terephthalate) was added to this mixture and subsequently heated to 250 ° C. When the temperature reached 250 ° C., vacuum was applied and the batch was held at 5 mm Hg for 5 hours and then discharged. The resulting polymer exhibited excellent fiber sizing properties. Example 9: 400 g ethylene glycol, 171 g sodiosulfoisophthalic acid, 0.
08 g antimony trioxide and 0.6 g titanium (IV) (triethanolaminato) isopropoxide were heated to 185 ° C. and held for 30 minutes. Two
400 g of poly (ethylene terephthalate) containing 0 mol% ethylene isophthalate was added and the batch was heated to 240 ° C. Thereafter, a further 510 g of the above poly (ethylene terephthalate) was added to this mixture and subsequently heated to 250 ° C. When the temperature reached 250 ° C., a vacuum of 5 mm Hg was applied for 3 hours, followed by discharge of the polymer. The resulting polymer exhibited excellent fiber sizing properties.

─────────────────────────────────────────────────── ─── Continued front page    (81) Designated countries EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE, TR), OA (BF , BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, G M, KE, LS, MW, MZ, SD, SL, SZ, TZ , UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AG, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, B Z, CA, CH, CN, CR, CU, CZ, DE, DK , DM, DZ, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, J P, KE, KG, KP, KR, KZ, LC, LK, LR , LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, MX, MZ, NO, NZ, PL, PT, R O, RU, SD, SE, SG, SI, SK, SL, TJ , TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW F term (reference) 4J029 AA03 AB04 AC02 AE02 AE18                       BA02 BA03 BA04 BA05 BA07                       BA08 BA10 BD04A CA02                       CA04 CA05 CA06 CB04A                       CB05A CB05B CB06A CH02                       DB02 FB07 FB17 HA01 HB01                       HB03A HD07 JE162 JE182                       KB14 KB23 KD01 KD07 KE02                       KE03

Claims (39)

[Claims] 1. A process for preparing a sulfonated polyester compound suitable for use as an antifouling agent or a fiber sizing agent: a) Formula (I): (Wherein, X is a cation, R is an aryl group optionally substituted with an alkyl group or an aryl group, Y is selected from the group consisting of hydrogen and an alkyl group, and n is a positive integer. At least one compound having the formula (II) (Wherein R ₁ is selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group each of which may be substituted with an alkyl group or an aryl group, and m
Is a positive integer. ) To produce at least one ester compound intermediate, and b) the ester compound intermediate is reacted with homo- or co-poly (ethylene terephthalate) to provide a sulfonated polyester. The above method comprising the step of producing a compound. 2. The method of claim 1, wherein X is selected from the group consisting of sodium, lithium, potassium, NH ₄ and tetrabutylphosphonium. 3. The method of claim 2, wherein X is sodium. 4. The method of claim 1, wherein R is phenyl or naphthyl. 5. The method of claim 1, wherein Y is an alkyl group selected from the group consisting of methyl, ethyl, propyl and butyl. 6. The method of claim 5, wherein Y is methyl. 7. The method of claim 1, wherein Y is hydrogen. 8. The method of claim 1, wherein n is 1-4. 9. The method of claim 8, wherein n is 1 or 2. 10. The method of claim 9, wherein n is 2. 11. The compound of formula (I) is dimethyl-5-sodiosulfoterephthalate, 5-sodiosulfoisophthalic acid, 5-lysoisophthalic acid, 3-sodiosulfobenzoic acid, 4-sodisosulfo-2,2-. Naphthalene dicarboxylic acid and 4
-Selected from the group consisting of sodiosulfodiphenyl-4,4'-dicarboxylic acid,
The method of claim 1. 12. The method according to claim 1, wherein R ₁ is an alkyl group having ₁ to 8 carbon atoms. 13. The method according to claim 12, wherein R ₁ is an alkyl group selected from the group consisting of methyl, ethyl, propyl and butyl. 14. The method of claim 1, wherein R ₁ is phenyl or naphthyl. 15. The method of claim 1, wherein R ₁ is a cycloalkyl group having 5-8 carbon atoms. 16. The method of claim 1, wherein m is 1-4. 17. The method of claim 13, wherein m is 2. 18. The compound of formula (II) is ethylene glycol, 1,2-propylene glycol, 1,3-propanediol, neopentyl glycol, glycerol, 1,2-butylene glycol, 1,4-butanediol, 2,2-
Dimethyl-1,3-propanediol, 1,6-hexanediol and 1,4
A method according to claim 1 selected from the group consisting of cyclohexanedimethanol. 19. The method of claim 1, comprising performing the reaction of step (a) at a temperature of about 120-280 ° C. 20. The method of claim 1, wherein the reaction of step (a) is carried out at a temperature of about 130-190 ° C. 21. The method according to claim 19, further comprising performing the reaction of step (a) in the presence of an esterification catalyst or a transesterification catalyst. 22. The method of claim 1, comprising performing the reaction of step (b) at a temperature of about 150-280 ° C. 23. The method of claim 22, wherein the reaction of step (b) is carried out at a temperature of about 180-260 ° C. 24. The method of claim 22, further comprising performing the reaction under a reduced pressure of about 600-0.5 mmHg. 25. Homo- or co-poly (ethylene terephthalate) is a copolymer of poly (ethylene terephthalate) with a comonomer selected from the group consisting of isophthalate, diethylene glycol, propylene glycol and 1,4-cyclohexanedimethanol. The method of claim 1, wherein the method is coalesced. 26. The step (a) comprises converting the compounds of the formulas (I) and (II) to the formula (III): (Wherein R ₂ is selected from the group consisting of an alkyl group and an aryl group optionally substituted with an alkyl group or an aryl group, Z is selected from the group consisting of hydrogen and an alkyl group, and p is a positive value. The method of claim 1, further comprising reacting in the presence of at least one compound having an integer. 27. R ₂ is an alkyl group having 1 to 12 carbon atoms,
27. The method of claim 26. 28. The method of claim 26, wherein Z is an alkyl group having 1 to 4 carbon atoms. 29. The method of claim 26, wherein R ₂ is phenyl or naphthyl. 30. The method of claim 26, wherein p is 1 or 2. 31. A compound of formula (III) is terephthalic acid, isophthalic acid,
Orthophthalic acid, 1,2-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,6-naphthalenedicarboxylic acid,
1,7-naphthalenedicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 2,3-
27. The method of claim 26, selected from the group consisting of naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid and their corresponding alkyl esters. 32. Step (a) comprises the step of converting the compounds of formula (I) and (II) into formula (IV) Wherein R ₃ and R ₄ are each independently selected from the group consisting of hydrogen and an alkyl group, and q is a positive integer. The method of claim 1, further comprising: 33. The method of claim 32, wherein R ₃ is an alkyl group having 1 to 4 carbon atoms. 34. R ₄ is an alkyl group having 1 to 12 carbon atoms,
The method of claim 32. 35. The method of claim 34, wherein R ₄ is methyl or lauryl. 36. The method of claim 32, wherein q is 2-20. 37. The method of claim 32, wherein the compound of formula (IV) is selected from the group consisting of polyethylene glycol, polypropylene glycol, block copolymers of polyethylene glycol and polypropylene glycol and their alkyl monoethers. . 38. The method of claim 1, comprising intermittently adding homo- or co-poly (ethylene terephthalate) to the ester compound intermediate. 39. The method according to claim 1, comprising continuously adding homo- or co-poly (ethylene terephthalate) to the ester compound intermediate.