JP2003525989A - Chain extension method - Google Patents

Abstract

(57) [Summary] The present invention provides a method for producing a high-molecular polymer by contacting a difunctional low-molecular polymer having a functional terminal group of —OH or —NH ₂ group with carbonyl bislactamate in a melt. Wherein the melt also contains an acid or base as a catalyst. If the bifunctional polymer contains -COOH groups, the melt preferably also contains bisoxazine or bisoxazoline.

Description

Detailed Description of the Invention

TECHNICAL FIELD The present invention relates to a difunctional polymer having a low molecular weight, which has a terminal functional group of —OH or —NH ₂ group in a melt by the following formula:

[0002]

[Chemical 2]

[In the formula, n is an integer of 3 to 15] The present invention relates to a method for producing a high molecular weight polymer by contacting with carbonylbislactamate (CBL). Preferably, the carbonylbislactamate is carbonylbiscaprolactamate (CBC) (n = 5).

A similar method is disclosed in WO 98/47940. WO 98/47940 is
It describes a method of making a high molecular polyamide by contacting a polyamide having a low molecular weight with carbonylbiscaprolactamate (CBC).

[0005]   The disadvantage of that method is that the reaction proceeds relatively slowly.

The object of the present invention is to provide a method which does not have the above-mentioned drawbacks or to a lesser extent the above-mentioned drawbacks.

This object is achieved by a melt which also contains an acid or a base. The acid or base has a catalytic function.

This ensures that the reaction proceeds more rapidly, as evidenced by the fact that the rate increases much faster with the catalyst than without the catalyst. This can be achieved, for example, by increasing the torque of a Brabender, which kneads a mixture of difunctional polymer and CBL, optionally in the presence of acid or base.

Suitable acids for use as catalysts for chain extension in the presence of CBL are LiX, Sb ₂ O ₃ , GeO ₂ and As ₂ O ₃ , BX ₃ , MgX ₂ , BiX ₃ , SnX ₄ , S.
bX ₅ , FeX ₃ , GeX ₄ , GaX ₃ , HgX ₂ , ZnX ₂ , AlX ₃ , Ti.
X ₄ , MnX ₂ , ZrX ₄ , R ₄ NX, R ₄ PX, HX (where X = I, Br
, Cl, F, OR and R = alkyl or aryl). H ₂ SO ₄ , H
_{NO 3, HX, H 3 PO} 4, H 3 PO 3, RH 2 PO 2, RH 2 PO 3, R [(C
Bronsted acids such as O) OH] _n (n = 1-6) are also suitable.

Suitable bases for use as catalysts for chain extension in the presence of CBC are Li-versetate, Zn acetylacetone (acac), M (OH) _n , (RO) _n.
M (M = alkali or alkaline earth, R = C ₁ -C ₂₀ alkyl or aryl
), NR _n H _{4 -n} OH (R = C ₁ -C ₂₀ alkyl or aryl), triamine
(Eg, triethylamine, tributylamine, trihexylamine, trioctylamine) and cyclic amines (eg, diazobicyclo [2,2,2] octane (
DABCO), dimethylaminopyridine (DMAP)), guanidine, morpholine,
Dibutyltin dilaurate (DBTDL), dibutyltin bis (2-ethylhexanoate), dibutyltin dibutyrate, dibutyltin dimethylate, dibutyltin dioctanoate.

The catalyst is preferably a Lewis acid or a Lewis base. This ensures that the time required for curing is even shorter.

The Lewis acid or base is preferably tetraalkoxy titanate, Zr (OR) ₄ , Li versetate, ZnAcAc (wherein the alkoxy group is, for example, butoxy group or isopropoxy group).

The amount of carbonylbiscaprolactamate used in the method of the present invention can vary within wide limits. Generally, at least about 0.1% by weight, based on the functional polymer, is required to have a significant effect. The amount exceeding 3% by weight is usually
Does not lead to a further increase in molecular weight.

Those skilled in the art will generally adjust the amount of carbonylbislactamate to accommodate the number of functional groups available and the required rate increase resulting from the increased molecular weight. Those of ordinary skill in the art will usually determine the optimal amount for the situation by simple experimentation.

By bifunctional polymer is meant hereinafter a polymer having two functional groups per molecule consisting of —OH groups or —NH ₂ groups.

Examples of such polymers are polyamides, polyesters, polycarbonates and polyether polyols.

The method of the invention can in principle be applied to all types of polyamides. These include at least aliphatic polyamides, such as polyamide-
4, polyamide-6, polyamide-8, polyamide-4,6, polyamide-6,6, polyamide-6,10, polyamides derived from aliphatic diamines and aromatic dicarboxylic acids, for example polyamide-4, T , Polyamide-6, T, polyamide-4, I (where T is terephthalate, I is isophthalate), copolyamides of linear polyamides, and copolyamides of aliphatic polyamides and partially aromatic polyamides, Examples include polyamide-6 / 6, T and polyamide-6 / 6, I.

Suitable polyesters for applying the process of the invention are at least polyesters derived from aliphatic dicarboxylic acids and diols, polyesters of aliphatic and cycloaliphatic diols with aromatic dicarboxylic acids, partial aliphatics. And partially aromatic copolyesters and polyesters containing units derived from cycloaliphatic dicarboxylic acids. Examples are polybutylene adipate, polymethylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, copolyesters of polybutylene adipate and polybutylene terephthalate, and polyesters derived from butanediol and cyclohexanedicarboxylic acid. is there.

The polyether polyol to which the method of the present invention may be applied is a polyol having a polyoxyalkylene structure and comprising an oxyalkylene group having 1 to 10 carbon atoms and oxygen atoms as repeating units, A diol is preferable. Examples of polyether polyols are polyoxymethylene, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyheptamethylene glycol, polyhexamethylene glycol and polydecamethylene glycol.

The process of the invention is carried out using conventional techniques and melt mixing equipment, eg in the solid phase with a low molecular weight polyamide, carbonylbislactamate and optionally other additives, eg in a tumble dryer. After mixing in, it is easily carried out by melting the resulting mixture in a conventional melt mixer, for example a Haake kneader, a Brabender mixer or a twin-screw or twin-screw extruder. be able to. The various ingredients may be added separately to the mixing device.

The carbonylbislactamate and catalyst may be added to the polymer product stream of the functional polymer having a low molecular weight as it exits the polymerization reactor in which the polymer was polymerized.

The polymerization process can be operated batchwise or continuously. In the former case, the residence time in the reactor can be shortened and thus the productivity can be increased, and
The step after condensation can be omitted.

In the method of the present invention, CBL reacts only with —NH ₂ groups or —OH functional groups of the functional polymer. Functional polymers that also have -COOH functionality include -OH functional groups or
Reacts with any of the NH ₂ functional groups. It is preferred that bisoxazine or bisoxazoline is present in the process of the invention, as well as CBL and catalyst, if the -COOH functionality is present in the melt. This ensures that the reaction proceeds even more rapidly.

The bisoxazoline is preferably 1,4-phenylenebisoxazoline.

[0025]   The present invention will be described based on the following examples.

Example 1 CBC is added to ground and dried PET (having two —OH end groups and a relative viscosity of η = 1.59) in a molar ratio of 1: 2 (CBC: PET). 1wt with respect to the amount of CBC
% Catalyst was added. All PET samples were tested on a laboratory extruder for 15g samples at 28
Extrusion was carried out at 0 ° C. and a residence time of 4 minutes. The obtained viscosities are shown in Table 1.

[0027]

[Table 1]

Comparative Experiment A Example 1 was repeated without the addition of catalyst. The relative viscosity rose from 1.59 to 1.76.

From these experiments, in a method of producing a high molecular weight polymer by contacting a difunctional low molecular weight polymer with carbonylbislactamate in a melt, the addition of acid and base uses acid or base. Faster increase in molecular weight than if not,
It can thus be concluded that it leads to chain extension.

Furthermore, it may be concluded that it is preferable to add lithium chloride, zirconium (IV) butoxide, zirconium acetylacetonate or lithium versetate.

─────────────────────────────────────────────────── ─── 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 (72) Inventor Bartholomes Johannes Margreta             Plum             Netherlands, Nuel-6235 Aye U             Restrainen, Klein Berg Hemau             Jech No. 52 F-term (reference) 4J031 CA06 CB00 CB04 CD18 CD19

Claims (4)

[Claims] 1. A difunctional low molecular weight polymer in the melt whose terminal functional groups are --OH or --NH ₂ groups is represented by the following formula: [In the formula, n is an integer of 3 to 15] A method for producing a high molecular polymer by contacting with carbonylbislactamate represented by the formula, characterized in that the melt also contains an acid or a base. Method. 2. The method according to claim 1, wherein the catalyst is a Lewis acid or a Lewis base. 3. The method according to claim 1, wherein the carbonylbislactamate is carbonylbiscaprolactamate. 4. A process according to claim 1, wherein the bifunctional polymer also contains --COOH groups and the bisoxazine or bisoxazoline is also present in the melt.