阅读说明：本技术 聚酯 (polyester ) 是由 M·B·席克 山本基仪 于 2018-05-02 设计创作，主要内容包括：本发明涉及一种由如下重复单元组成的聚酯：(A)衍生自酸组分的重复单元,所述酸组分由(a1)2,5-呋喃二甲酸,(a2)一种脂族C<Sub>4</Sub>-C<Sub>36</Sub>二羧酸或多种脂族C<Sub>4</Sub>-C<Sub>36</Sub>二羧酸的混合物和(a3)含磺酸根的二羧酸；以及(B)衍生自二醇/胺组分的重复单元,和任选的其他重复单元(C)和/或支化组分(E)以及(D)衍生自至少一种选自二异氰酸酯或低聚异氰酸酯和二异氰脲酸酯或低聚异氰脲酸酯的二或寡官能化合物的重复单元。本发明还涉及所述聚酯的制备及其用途。(The invention relates to a polyester consisting of the following repeating units: (A) repeating units derived from an acid component consisting of (a1)2, 5-furandicarboxylic acid, (a2) an aliphatic C 4 ‑C 36 Dicarboxylic acids or a plurality of aliphatic C 4 ‑C 36 A mixture of dicarboxylic acids and (a3) a sulfonate-containing dicarboxylic acid; and (B) repeating units derived from a diol/amine component, and optionallyFurther repeating units (C) and/or branching components (E) and (D) repeating units derived from at least one di-or oligofunctional compound selected from diisocyanates or oligoisocyanates and diisocyanurates or oligoisocyanurates. The invention also relates to the preparation of said polyesters and to the use thereof.)

1. A polyester consisting of the following repeating units:

A) A repeating unit derived from an acid component consisting of:

a1) from 30 to 90 mol%, based on the sum of components a1, a2 and a3, of 2, 5-furandicarboxylic acid,

a2) 0 to 60 mol%, preferably 0 to 50 mol%, based on the sum of components a1, a2 and a3, of an aliphatic C₄-C₃₆Dicarboxylic acids or a plurality of aliphatic C₄-C₃₆A mixture of dicarboxylic acids, and

a3) 10 to 60 mol%, based on the sum of components a1, a2 and a3, of a sulfonate-containing dicarboxylic acid,

Wherein the molar percentages of components a1) to a3) add up to a total of 100 mol%,

Of these, preference is given to a proportion of a1 of 55 to 85 mol%, a2 of 0 to 30 mol% at the same time, a3 of 15 to 45 mol% at the same time,

B) Repeating units derived from a diol/amine component consisting of:

b1) C₂-C₁₂alkanediol or C' s₂-C₁₂A mixture of alkanediols, and/or

b2) A dihydroxy compound or mixture of such dihydroxy compounds of formula I:

HO-[(CH₂)_n-O]_m-H (I)

wherein n is 2, 3 or 4, m is an integer from 2 to 250,

b3) Optionally one or more amino groups C₂-C₁₂alkanols or one or more amino groups C₅-C₁₀a cycloalkanol or a mixture thereof, and

b4) Optionally one or more diamino C₁-C₈the alkane is selected from the group consisting of alkanes,

Wherein the amount of B is chosen such that for every 100 moles of A there are 100 moles of B, minus the moles of D and E,

And wherein the sum of the proportions of B1 and B2 in B is at least 50 mol%, preferably at least 80 mol%, C) optionally recurring units derived from:

c1) One or more hydroxycarboxylic acids of the formula IIa:

HO-C(O)-G-OH (IIa)

Wherein G represents a group selected from phenylene, - (CH)₂)_q-, -C (R) H-and C (R) HCH₂The group of (a) or (b),

Wherein q is an integer from 1 to 5, wherein R is methyl or ethyl, and/or

c2) One or more aminocarboxylic acids or cyclic amides thereof selected from caprolactam, 1, 6-aminocaproic acid, laurolactam, 1, 12-aminolauric acid and 1, 11-aminoundecanoic acid,

Wherein the proportion of C in the total mass of the polyester is preferably not more than 20% by weight, particularly preferably not more than 10% by weight,

D) 0.1% to 4% by weight, based on the sum of components A, B and C, of repeating units derived from at least one di-or oligofunctional compound selected from diisocyanates or oligoisocyanates and diisocyanurates or oligoisocyanurates, and

E) 0.1 to 4 wt.%, based on the sum of components A, B and C, of repeating units derived from a branched component comprising at least 3 functional groups selected from COOH, OH, NH₂And mixtures thereof.

2. The polyester of claim 1, wherein the sum of the proportions of a2, b3, b4, c1 and c2 is not more than 10% by weight, preferably not more than 5% by weight, particularly preferably 0% by weight, based on the total mass of the polyester.

3. Polyester according to claim 1 or 2, wherein a3 is a sulfonate-containing aromatic dicarboxylic acid, wherein the sulfonate is present in the form of the free acid or salt, preferably in the form of an alkali metal salt, in particular in the form of a sodium salt.

4. A polyester as claimed in claim 3, wherein a3 is selected from 1, 4-benzenedicarboxylic acid-2-sulfonic acid, 1, 3-benzenedicarboxylic acid-5-sulfonic acid (also known as isophthalic acid-5-sulfonic acid), 1, 2-benzenedicarboxylic acid-3-sulfonic acid and 1, 2-benzenedicarboxylic acid-4-sulfonic acid, in each case in the form of the free acid or salt, preferably in the form of an alkali metal salt, in particular the sodium salt, particularly preferably the monosodium salt of isophthalic acid-5-sulfonic acid.

5. The polyester according to any of claims 1 to 4, wherein b1 is selected from ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 2, 4-dimethyl-2-ethylhexane-1, 3-diol, 2-dimethyl-1, 3-propanediol, 2-ethyl-2-butyl-1, 3-propanediol, 2-ethyl-2-isobutyl-1, 3-propanediol, 1, 6-hexanediol, 1, 8-octanediol and 2,2, 4-trimethyl-1, 6-hexanediol, wherein b1 is preferably selected from ethylene glycol, 1, 4-butanediol, 1, 6-hexanediol and 1, 8-octanediol.

6. The polyester of any of claims 1 to 5, wherein b2 is selected from the group consisting of diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, polypropylene glycol and polytetrahydrofuran, wherein b2 is preferably selected from the group consisting of diethylene glycol, triethylene glycol and tetraethylene glycol.

7. The polyester as claimed in any of claims 1 to 6, wherein D is a repeating unit derived from an aliphatic diisocyanate, wherein the diisocyanate is preferably a linear or branched alkylene diisocyanate or cycloalkylene diisocyanate having in both cases from 2 to 20 carbon atoms, in particular from 3 to 15 carbon atoms, wherein D is particularly preferably 1, 6-hexamethylene diisocyanate.

8. The polyester according to any of claims 1 to 7, wherein E is a repeating unit derived from a branched component selected from the group consisting of tartaric acid, citric acid, malic acid, trimethylolpropane, trimethylolethane, pentaerythritol, polyether triols, glycerol, trimesic acid, trimellitic acid and pyromellitic acid, wherein E is preferably a repeating unit derived from trimethylolpropane, pentaerythritol or glycerol, wherein E is particularly preferably a repeating unit derived from glycerol.

9. An aqueous solution comprising the polyester according to any of claims 1 to 8, which is preferably a laminating adhesive.

10. a personal care formulation comprising a polyester according to any of claims 1 to 8, preferably a hair styling composition.

11. Use of the aqueous solution of claim 9 as a laminating adhesive.

12. use of the polyester according to any of claims 1 to 8 or the formulation according to claim 10 for hair styling.

13. a process for preparing the polyester of any of claims 1-8, comprising:

Comprising the reaction of a mixture of an acid constituent as defined under A, a diol/amine constituent as defined under B, optionally a hydroxycarboxylic acid as defined under c1, optionally an aminocarboxylic acid and/or a cyclic amide as defined under c2, and a branching component as defined under E, wherein an intermediate is obtained,

removing from the intermediate any excess diol/amine component as defined under B, and

Reaction of the intermediate with a compound as defined under D,

Wherein a1, a2 and a3 are each used independently in the form of the free dicarboxylic acids or dialkyl esters, in particular in the form of dimethyl esters,

and wherein b1, b2, b3 and b4 are used in the underivatized form as defined under b1, b2, b3 and b4,

And wherein c1 is used in the form of the free hydroxycarboxylic acid or in the form of the formula IIa or IIb,

Wherein p is an integer of 1 to 1500, r is an integer of 1 to 4, and G represents a group selected from phenylene, - (CH)₂)_q-, -C (R) H-and-C (R) HCH₂Wherein q is an integer of 1 to 5, wherein R is methyl or ethyl,

And wherein c2 is used in the form of the free aminocarboxylic acid or its cyclic amide,

and wherein D is used in the underivatized form of diisocyanates or oligoisocyanates or diisocyanurates or oligoisocyanurates,

And wherein E is used in underivatized form.

Examples

Name, abbreviation and molar Mass M (g/mol)

Test method

The properties of the polyesters prepared according to the examples were tested using the following methods: when reference is made herein to a standard, it is in each case to refer to a version of the standard that is valid 8 months and 1 day 2016.

Viscosity number VN according to EN-ISO 1628-1: 2012-10, capillary viscometry. An Ubbelohde M-II microscopic viscometer was used. The solvent used was a phenol/o-dichlorobenzene mixture (50/50 wt/wt).

modulus of elasticity and yield stress according to ISO 527-3: 2003 was determined by tensile testing using tensile bars having a thickness of about 420 μm.

Glass transition temperature Tg to DIN EN ISO 11357-3: 2913-04.

General preparation of polyestersMethod of producing a composite material

The mol% values shown below are based on the sum of the moles of dimethyl furandicarboxylate and sodium dimethyl sulfoisophthalate, which is set at 100 mol%.

To prepare the polyester, 70 mol% of dimethyl-2, 5-furandicarboxylate, 30 mol% of sodium dimethyl sulfoisophthalate, 130 mol% of the specified diol and optionally the specified amount of glycerol were mixed with the specified amount of tetrabutylorthotitanate (TBOT). The reaction mixture was heated to a temperature of 180 ℃ and reacted at this temperature for 2 hours. The temperature was then raised to 240 ℃ and the excess diol was distilled off under vacuum over 1-2 hours. The optionally specified amount of hexamethylene diisocyanate was then added slowly over 10 minutes at 240 ℃.

in this process, TBOT acts as a polycondensation catalyst. Glycerol was used as the branching component and HDI was used as the "chain extender". After the addition of HDI, the polyester chains present react with HDI via their terminal OH groups and form urethane groups. This increases the average molar mass of the polyester.