Process for the preparation of TPU alloy by in-situ reactive compatibility technology

Abstract

A process for preparing a TPU alloy material through in-situ compatibilization includes: 1) adding a premixed TPU raw material to a feeding port of a twin-screw extruder; injecting a mixture of an alloy component and a dual-active substance into the twin-screw extruder through a lateral feeding port; adding an auxiliary reagent to the TPU raw material or the mixture of the alloy component and the dual-active substance, wherein the alloy component is a polyolefin or a thermoplastic polymer material having reactivity, wherein the dual-active substance is a substance containing a group reactive with the TPU raw material and a group reactive with the alloy component, and the auxiliary reagent includes an initiator; 2) controlling a temperature of a reaction zone of the twin-screw extruder at 50° C. to 250° C., and granulating an extruded material by underwater cutting; and 3) drying the granulated product to obtain the TPU alloy material.

Claims

1. A process for preparing a thermoplastic polyurethane (TPU) alloy material through in-situ compatibilization, comprising: 1) adding premixed 100 parts by weight of unreacted TPU raw material to a feeding port of a twin-screw extruder; injecting a mixture of 5 to 95 parts by weight of an alloy component and 0.1 to 10 parts by weight of a dual-active substance into the twin-screw extruder through a lateral feeding port; adding 0.1 to 5 parts by weight of an auxiliary reagent to the unreacted TPU raw material or the mixture of the alloy component and the dual-active substance, wherein the alloy component is a polyolefin material or a thermoplastic polymer material having reactivity, wherein the dual-active substance is a substance containing a group reactive with the unreacted TPU raw material and a group reactive with the alloy component, and wherein the auxiliary reagent comprises an initiator; 2) controlling a temperature of a reaction zone of the twin-screw extruder at 50° C. to 250° C., and granulating an extruded material by underwater cutting to produce a granulated product; and 3) drying the granulated product obtained in step 2) to obtain the TPU alloy material.

2. The process according to claim 1, wherein the dual-active substance is a compound containing one or more functional group selected from the group consisting of an anhydride group, a carboxyl (—COOH) group, a hydroxyl (—OH) group, an amino (—NH or —NH.sub.2) group, an isocyanate group (—NCO) group, and an epoxy group.

3. The process according to claim 2, wherein the dual-active substance is one selected from the group consisting of maleic anhydride, glycidyl methacrylate, acrylic acid, methyl methacrylate, butyl acrylate, acrylamide, allyl polyethylene glycol, amino acid, and epoxy resin.

4. The process according to claim 1, wherein the thermoplastic polymer material having reactivity is one selected from the group consisting of polyamide, acrylonitrile-butadiene-styrene (ABS) resin, thermoplastic elastomer (TPE), and polyacrylate.

5. The process according to claim 1, wherein the polyolefin material is one selected from the group consisting of styrene-ethylene/butylene-styrene copolymer (SEBS), poly(styrene-butadiene-styrene) (SBS), polypropylene (PP), polyethylene (PE), ethylene-vinyl acetate (EVA), polyolefin (POE), and ethylene propylene diene monomer (EPDM).

6. The process according to claim 1, wherein the unreacted TPU raw material comprises a polymeric polyol, a chain extender, and an isocyanate.

7. The process according to claim 6, wherein the polymeric polyol is one or more selected from the group consisting of a polyester polyol, a polyether polyol, and hydroxyl terminated polybutadiene diol, and the chain extender is a small molecule diol or diamine having 12 carbon atoms or less.

8. The process according to claim 6, wherein the chain extender is one or more selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, neopentyl glycol, and dipropylene glycol; wherein the isocyanate is one or more selected from the group consisting of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), and xylylene diisocynate (XDI).

9. The process according to claim 1, wherein the auxiliary reagent further comprises an antioxidant, a lubricant, and an UV-resistant additive.

10. The process according to claim 1, wherein a rotation speed of the screw extruder in step 2) is controlled to be 80 rpm to 400 rpm, and a temperature in a cooling zone is controlled to be at 90° C. to 110° C.

11. The process according to claim 7, wherein the chain extender is one or more selected from the group consisting of ethylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, diethylene glycol, triethylene glycol, neopentyl glycol, and dipropylene glycol; wherein the isocyanate is one or more selected from the group consisting of toluene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), dicyclohexylmethane diisocyanate (H12MDI), isophorone diisocyanate (IPDI), and xylylene diisocynate (XDI).

Description

EXAMPLE 1

(1) A process for preparing a TPU alloy material through in-situ compatibilization comprises the following steps:

(2) 1) pre-mixing 68 parts of polyester polyol having a molecular weight of 2000 g/mol, 6 parts of butanediol (BDO), and 26 parts of diphenylmethane diisocyanate (MDI) in a reaction kettle; then adding the mixture to a feeding port of a twin-screw extruder; and injecting 95 parts of SEBS (YH-503T from Yueyang Petrochemical, Yueyang, Hunan, China), 10 parts of MAH (maleic anhydride), and 0.1 part of the initiator DCP (dicumyl peroxide) into the twin-screw extruder through a lateral feeding port;

(3) 2) controlling a temperature of a reaction zone of the twin-screw extruder to be at 140° C. to 200° C., and a temperature of a cooling zone to be at 90° C. to 110° C., and then granulating/pelletizing the extruded material by underwater cutting (wet cut strand pelletizing); and

(4) 3) drying the granulated product obtained in step 2) to obtain the TPU alloy material.

(5) The TPU modified material prepared in this Example has a hardness of 75 A, a tensile strength of 10.2 MPa, a DIN abrasion of 55 mm.sup.3 and a ball rebound of 55%.

EXAMPLE 2

(6) A process for preparing a TPU alloy material through in-situ compatibilization comprises the following steps:

(7) 1) adding 0.3 part of Irganox® 1010 (BASF Corp), 0.2 part of Irganox® 1076 (BASF Corp), 0.5 part of Tinuvin® B900 (BASF Corp), 0.3 part of E wax (emulsifying wax), and 0.2 part of oleylamide (oleamide) to a mixture of 55 parts of polyester polyol having a molecular weight of 1500 g/mol, 7 parts of BDO, and 38 parts of diphenylmethane diisocyanate (MDI), and pre-mixing the mixture in a reaction kettle, then adding the mixture to a feeding port of a twin-screw extruder, and injecting 75 parts of SEBS (G1650 from Kraton Corp., Houston, Tex.), 5 parts of MAH (maleic anhydride) and 0.2 part of the initiator DCP (dicumyl peroxide) into the twin-screw extruder through a lateral feeding port;

(8) 2) controlling a temperature of a reaction zone of the twin-screw extruder to be at 50° C. to 250° C., and a temperature of a cooling zone to be at 90° C. to 110° C., and then granulating the extruded material by underwater cutting (wet cut pelletizing); and

(9) 3) drying the granulated product obtained in step 2) to obtain the TPU alloy material.

(10) The TPU modified material prepared in this Example has a hardness of 82 A, a tensile strength of 9.9 MPa, a DIN abrasion of 43 mm.sup.3 and a ball rebound of 50%.

EXAMPLE 3

(11) A process for preparing a TPU alloy material through in-situ compatibilization comprises the following steps:

(12) 1) adding 0.3 part of Irganox® 1010, 0.1 part of Irganox® 1076, 0.7 part of Tinuvin® B900, 0.2 part of octadecanamide, and 0.4 part of EBS to 70 parts of polyester polyol having a molecular weight of 1800 g/mol, and then pre-mixing with 5 parts of BDO and 25 parts of toluene diisocyanate (TDI) in a reaction kettle; then adding the mixture to a feeding port of a twin-screw extruder; and injecting 65 parts of EVA (Evaflex® 150Y from Mitsui Chemicals), 0.1 part of acrylic acid, and 0.1 part of the initiator DCP (dicumyl peroxide) into the twin-screw extruder through a lateral feeding port;

(13) 2) controlling a temperature of a reaction zone of the twin-screw extruder to be at 140° C. to 180° C., and a temperature of a cooling zone to be at 90° C. to 110° C., and then granulating the extruded material by underwater cutting; and

(14) 3) drying the granulated product obtained in step 2) to obtain the TPU alloy material.

(15) The TPU modified material prepared in this Example has a hardness of 81 A, a tensile strength of 12.9 MPa, a DIN abrasion of 66 mm.sup.3 and a ball rebound of 53.9%.

EXAMPLE 4

(16) A process for preparing a TPU alloy material through in-situ compatibilization comprises the following steps:

(17) 1) adding 0.35 part of Irganox® 1010, 0.2 part of Irganox® 1098, 0.2 part of Tinuvin® 770, 0.4 part of Chimassorb® 2020 (BASF), 0.4 part of oleylamide, and 0.1 part of octadecanamide to 45 parts of polyester polyol having a molecular weight of 1000 g/mol, then pre-mixing the resulting mixture with 8 parts of BDO and 47 parts of toluene diisocynate (TDI) in a reaction kettle; then adding the mixture to a feeding port of a twin-screw extruder; and injecting 34 parts of POE (8130 from Dow Chemicals), 0.5 part of acrylamide, and 0.15 part of the initiator DCP (dicumyl peroxide) into the twin-screw extruder through a lateral feeding port;

(18) 2) controlling a temperature of a reaction zone of the twin-screw extruder to be at 140° C. to 170° C., and a temperature of a cooling zone to be at 90° C. to 110° C., and then granulating the extruded material by underwater cutting; and

(19) 3) drying the granulated product obtained in step 2) to obtain the TPU alloy material.

(20) The TPU modified material prepared in this Example has a hardness of 79 A, a tensile strength of 7.6 MPa, a DIN abrasion of 44.2 mm.sup.3 and a ball rebound of 59.1%.

EXAMPLE 5

(21) A process for preparing a TPU alloy material through in-situ compatibilization comprises the following steps:

(22) 1) adding 0.35 part of Irganox® 1010, 0.2 part of Irganox® 1098, 0.3 part of Tinuvin® 770, 0.2 part of Chimassorb® 2020, 0.4 part of oleylamide, and 0.1 part of octadecanamide to 45 parts of polyester polyol having a molecular weight of 1800 g/mol, then pre-mixing the resulting mixture with 8 parts of BDO and 47 parts of hexamethylene diisocyanate (HDI) in a reaction kettle, then adding the mixture to a feeding port of a twin-screw extruder, and injecting 45 parts of POE (8130 from Dow Chemicals), 1.5 parts of acrylamide and 0.25 part of the initiator DCP (dicumyl peroxide) into the twin-screw extruder through a lateral feeding port;

(23) 2) controlling a temperature of a reaction zone of the twin-screw extruder to be at 140° C. to 170° C., and a temperature of a cooling zone to be at 90° C. to 110° C., and then granulating the extruded material by underwater cutting; and

(24) 3) drying the granulated product obtained in step 2) to obtain the TPU alloy material.

(25) The TPU modified material prepared in this Example has a hardness of 73 A, a tensile strength of 13.4 MPa, a DIN abrasion of 56.1 mm.sup.3 and a ball rebound of 53.1%.

EXAMPLE 6

(26) A process for preparing a TPU alloy material through in-situ compatibilization comprises the following steps:

(27) 1) adding 0.55 part of Irganox® 1010, 0.2 part of Irganox® 1098, 0.25 part of Tinuvin® 770, 0.5 part of Chimassorb® 2020, 0.4 part of oleylamide and 0.1 part of octadecanamide to 45 parts of polyester polyol having a molecular weight of 1800 g/mol, then pre-mixing the resulting mixture with 8 parts of BDO and 47 parts of hexamethylene diisocyanate (HDI) in a reaction kettle, then adding the mixture to a feeding port of a twin-screw extruder, and injecting 5 parts of polyamide, 0.1 part of methyl methacrylate and 1 part of the initiator DCP (dicumyl peroxide) into the twin-screw extruder through a lateral feeding port;

(28) 2) controlling a temperature of a reaction zone of the twin-screw extruder to be at 140° C. to 170° C., and a temperature of a cooling zone to be at 90° C. to 110° C., and then granulating the extruded material by underwater cutting; and

(29) 3) drying the granulated product obtained in step 2) to obtain the TPU alloy material.

(30) The TPU modified material prepared in this Example has a hardness of 78 A, a tensile strength of 13.4 MPa, a DIN abrasion of 56.1 mm.sup.3 and a ball rebound of 52.9%.

EXAMPLE 7

(31) A process for preparing a TPU alloy material through in-situ compatibilization comprises the following steps:

(32) 1) adding 0.55 part of Irganox® 1010, 0.2 part of Irganox® 1098, 0.25 part of Tinuvin® 770, 0.5 part of Chimassorb® 2020, 0.4 part of oleylamide and 0.1 part of octadecanamide to 45 parts of polyester polyol having a molecular weight of 1800 g/mol, then pre-mixing the resulting mixture with 8 parts of BDO and 47 parts of hexamethylene diisocyanate (HDI) in a reaction kettle, then adding the mixture to a feeding port of a twin-screw extruder, and injecting 75 parts of ABS resin, 6 parts of butyl acrylate, and 1 part of the initiator DCP (dicumyl peroxide) into the twin-screw extruder through a lateral feeding port;

(33) 2) controlling a temperature of a reaction zone of the twin-screw extruder to be at 140° C. to 170° C., and a temperature of a cooling zone to be at 90° C. to 110° C., and then granulating the extruded material by underwater cutting; and

(34) 3) drying the granulated product obtained in step 2) to obtain the TPU alloy material.

(35) The TPU modified material prepared in this Example has a hardness of 78 A, a tensile strength of 13.4 MPa, a DIN abrasion of 56.1 mm.sup.3 and a ball rebound of 52.9%.

EXAMPLE 8

(36) A process for preparing a TPU alloy material through in-situ compatibilization comprises the following steps:

(37) 1) adding 0.55 part of Irganox® 1010, 0.2 part of Irganox® 1098, 0.25 part of Tinuvin® 770, 0.5 part of Chimassorb® 2020, 0.4 part of oleylamide, and 0.1 part of octadecanamide to 45 parts of polyester polyol having a molecular weight of 1800 g/mol, then pre-mixing the resulting mixture with 8 parts of BDO and 47 parts of hexamethylene diisocyanate (HDI) in a reaction kettle, then adding the mixture to a feeding port of a twin-screw extruder, and injecting 25 parts of TPE, 2 parts of epoxy resin and 0.8 part of the initiator DCP (dicumyl peroxide) into the twin-screw extruder through a lateral feeding port;

(38) 2) controlling a temperature of a reaction zone of the twin-screw extruder to be at 140° C. to 170° C., and a temperature of a cooling zone to be at 90° C. to 110° C., and then granulating the extruded material by underwater cutting; and

(39) 3) drying the granulated product obtained in step 2) to obtain the TPU alloy material.

(40) The TPU modified material prepared in this Example has a hardness of 82 A, a tensile strength of 13.3 MPa, a DIN abrasion of 56.1 mm.sup.3 and a ball rebound of 53.5%.

(41) The TPU alloy material obtained in Example 3 is used in EVA foaming process to obtain an EVA foamed material. This EVA foamed material is compared with an EVA foamed material obtained by separately using TPU and EVA-g-MAH, and the results are shown in Table 1.

(42) TABLE-US-00001 TABLE 1 Performance test data of an EVA foam material obtained by a process of the present invention and that obtained by a traditional process Unit Example 3 Traditional Process Tensile strength MPa 8.4 6.1 Tear strength KN/m 13.2 10.2 Ball rebound % 69.2 63.6 Compression set % 26.3 33.2

(43) As can be seen from the data in Table 1, the EVA foamed material obtained with a TPU material of the present invention has a tensile strength increased by 2.3 MPa, a tear strength increased by 3 KN/m, a ball rebound may be increased by 5.6%, and a compression set reduced by 6.9%. It can be seen from the data that processes of the present patent have clear advantages in improving the performances of the final products, as compared with the traditional process.

(44) The above contents are merely preferred examples of the present invention and are not intended to limit the scope of the present invention. Any modification, equivalent displacement, improvement and the like, which fall within the spirit and principle of the present invention, should be included in the protection scope of the present invention.