阅读说明：本技术 聚噁唑烷酮的本体聚合 (Bulk polymerization of polyoxazolidinones ) 是由 P·德斯保斯 H-J·托马斯 于 2019-07-17 设计创作，主要内容包括：本发明涉及一种用于通过以下方式制备热塑性聚合物的方法：使至少组分(i)至(ii)：包含至少一种二异氰酸酯的多异氰酸酯组合物(i)；包含至少一种二环氧化物的环氧化物组合物(ii)；在催化剂组合物(iii)的存在下反应；其中在第一温度范围(T_1)内的温度下将环氧化物组合物(ii)和催化剂组合物(iii)作为混合物引入(a)；在保持温度在第一温度范围T_1内的同时,至少成比例地加入多异氰酸酯组合物(i)(b)；将温度升高到最终温度范围(T_f)内的温度(c)；以及在最终温度范围内,加入剩余的多异氰酸酯组合物(i)(d)。本发明还涉及一种使用该方法获得或可获得的热塑性聚合物,并且还涉及热塑性聚合物的用途,用于通过注塑、压延、粉末烧结、激光烧结、熔融压制或挤出制备纤维或成型体；或作为改性剂用于热塑性材料。(The invention relates to a method for producing thermoplastic polymers by: reacting at least components (i) to (ii): a polyisocyanate composition (i) comprising at least one diisocyanate; an epoxide composition (ii) comprising at least one diepoxide; (iv) in the presence of a catalyst composition (iii); wherein in a first temperature range (T) 1 ) Introducing an epoxide composition (ii) and a catalyst composition (iii) as a mixture into (a) at a temperature; in a first temperature range T 1 Simultaneously, at least proportionally adding the polyisocyanate composition (i) (b); increasing the temperature to a final temperature range (T) f ) The temperature (c) inside; and in the final temperature range, addingThe remaining polyisocyanate compositions (i) (d). The invention also relates to a thermoplastic polymer obtained or obtainable using this method, and also to the use of a thermoplastic polymer for producing fibers or shaped bodies by injection molding, calendering, powder sintering, laser sintering, melt pressing or extrusion; or as a modifier for thermoplastic materials.)

1. A method of making a thermoplastic polymer by: bringing at least components (i) to (ii)

i) A polyisocyanate composition comprising at least one diisocyanate;

ii) an epoxide composition comprising at least one diepoxide;

(iv) in the presence of a catalyst composition (iii); wherein

a) First in a first temperature range (T)₁) Charging the epoxide composition (ii) and the catalyst composition (iii) as a mixture at a temperature within;

b) in a first temperature range T₁Simultaneously at least partially adding a polyisocyanate composition (i);

c) increasing the temperature to a final temperature range (T)_f) The temperature inside;

d) the remaining polyisocyanate composition (i) is added in the final temperature range.

2. The method of claim 1, wherein the final temperature range T_fIncluding a second temperature range T₂And a third temperature range T₃Wherein the third temperature range T₃Above the second temperature range T₂And a second temperature range T₂Above the first temperature range T₁。

3. Method according to claim 1 or 2, wherein the first temperature range T₁140 to 180 ℃, preferablyPreferably from 150 to 170 deg.C, more preferably from 155 to 165 deg.C.

4. The method according to any one of claims 1 to 3, wherein the final temperature range T_fIs composed of>180 to 250 ℃, preferably>170 to 250 ℃, more preferably>165 to 250 ℃, wherein the second temperature range T is preferred₂Is composed of>180 to 200 ℃, preferably>170 to 200 ℃, more preferably>165 to 200 ℃, and a third temperature range T₃Is composed of>200 to 250 ℃, preferably>200 to 230 ℃.

5. The method of any one of claims 1 to 4, wherein according to (b), in the first temperature range T₁In addition, from 80% to 95% by weight of polyisocyanate composition (i) are added, based on the total amount of polyisocyanate composition (i).

6. The method according to any one of claims 1 to 5, wherein in the final temperature range T_f5 to 20% by weight, based on the total amount of polyisocyanate composition (i), preferably in the second temperature range T₂Adding from 5% to 20% by weight of a polyisocyanate composition (i), and in a third temperature range T₃Optionally, from 0% to 10% by weight, preferably 0% by weight, of the polyisocyanate composition (i) is added, in each case based on the total amount of polyisocyanate composition (i).

7. The process according to any one of claims 1 to 6, wherein catalyst composition (iii) comprises at least one ionic liquid, wherein the ionic liquid preferably comprises a heterocyclic cation or an ammonium cation, more preferably a cation selected from the group consisting of pyridinium, pyrazolinium, imidazolinium, imidazolium and ammonium, and a corresponding anion, preferably selected from the group consisting of halide, more preferably selected from chloride, bromide and iodide, more preferably chloride; wherein the at least one ionic liquid is more preferably selected from the group consisting of 1-ethyl-3-methylimidazolium bromide (EMIM-Br), 1-benzyl-3-methylimidazolium chloride (BEMIM-Cl), 1-butyl-1-methylpiperidinium chloride (BMPM-Cl), 1-ethyl-2, 3-dimethylimidazolium bromide (EDMIM-Br) and 1- (2-hydroxyethyl) -3-methylimidazolium chloride (HEMIM-Cl).

8. The process according to any one of claims 1 to 7, wherein the amount of polyisocyanate composition (i), epoxide composition (ii) and catalyst composition (iii) constitutes 95 wt%, preferably 98 wt% of the total reacted amount of all substances present.

9. A thermoplastic polymer obtained or obtainable by the process according to any one of claims 1 to 8.

10. A thermoplastic polymer obtained or obtainable by: bringing at least components (i) to (ii)

i) A polyisocyanate composition comprising at least one diisocyanate;

ii) an epoxide composition comprising at least one diepoxide;

(iv) in the presence of a catalyst composition (iii); wherein

a) First in a first temperature range (T)₁) Charging the epoxide composition (ii) and the catalyst composition (iii) as a mixture at a temperature within;

b) (ii) at least partially adding the polyisocyanate composition (i) while maintaining the first temperature;

c) increasing the temperature to a final temperature range (T)_f) The temperature inside;

d) (ii) adding the remaining polyisocyanate composition (i) in the final temperature range;

to obtain a thermoplastic polymer.

11. Thermoplastic polymer according to claim 10, wherein catalyst composition (iii) comprises at least one ionic liquid, wherein the ionic liquid preferably comprises a heterocyclic cation or an ammonium cation, more preferably a cation selected from the group consisting of pyridinium, pyrazolinium, imidazolinium, imidazolium and ammonium, and a corresponding anion, preferably selected from the group consisting of halide, more preferably selected from chloride, bromide and iodide, more preferably chloride; wherein the at least one ionic liquid is more preferably selected from the group consisting of 1-ethyl-3-methylimidazolium bromide (EMIM-Br), 1-benzyl-3-methylimidazolium chloride (BEMIM-Cl), 1-butyl-1-methylpiperidinium chloride (BMPM-Cl), 1-ethyl-2, 3-dimethylimidazolium bromide (EDMIM-Br) and 1- (2-hydroxyethyl) -3-methylimidazolium chloride (HEMIM-Cl).

12. Thermoplastic polymer according to claim 10 or 11, wherein the amount of polyisocyanate composition (i), epoxide composition (ii) and catalyst composition (iii) constitutes 95 wt%, preferably 98 wt% of the total reacted amount of all substances present.

13. Thermoplastic polymer according to any of claims 10 to 12, wherein the number average molar mass M of the thermoplastic polymer_nGreater than 10000g/mol, preferably greater than 15000g/mol, more preferably greater than 18000 g/mol.

14. Thermoplastic polymer according to any of claims 10 to 13, wherein the polydispersity is less than 4, preferably less than 3.5, wherein the polydispersity PI is the weight average molar mass M of the thermoplastic polymer_wWith number average molar mass M_nThe quotient of (a).

15. Use of a thermoplastic polymer obtained or obtainable by the process according to any one of claims 1 to 8 or the thermoplastic polymer according to any one of claims 10 to 14 for the preparation of fibers or shaped bodies by injection molding, calendering, powder sintering, laser sintering, melt pressing or extrusion; or as a modifier for thermoplastic materials.

Examples

1. Chemical product

2. Examples of the embodiments

2.1 example 1: reaction of bisphenol A diglycidyl ether with MDI with a temperature gradient during the addition of MDI

In a nitrogen box, 60g of diepoxide 1 and 0.084g of catalyst 1 were weighed into a 100ml glass vessel equipped with a magnetic stir bar and sealed. The mixture was removed from the nitrogen box and mixed on a magnetic stirrer at 80 ℃ for 3 hours.

Both extruder screws were inserted into a 15ml twin screw MC 15 High Torque and High Force (High Torque and High Force) micro compounder from Xplore and closed firmly with a Torque wrench (50 Nm). Heating to an external temperature of 100 ℃ is then carried out. Screw 2 closure plates onto the extruder. The rear panel has a joint for argon inerting. The front panel has an inlet for metering isocyanate.

A50 ml bottle containing diisocyanate 1 was melted in a drying oven at 70 ℃ for 1 hour.

12.2g of a warm mixture of diepoxide 1 and catalyst 1 are introduced into the extruder by briefly removing the front closing plate and heated to 100 ℃. After introduction, the insulation panels were reinstalled and the stirrer was started at 100 rpm. For inertization, the test specimen was covered with 20l/h of argon 4.6 from a gas cylinder. The temperature was raised from 100 ℃ to an external temperature of 160 ℃. The internal temperature adjustment took 5 minutes to reach 155 ℃. After this 5 minutes, 6.91ml of diisocyanate 1 were metered in using a LA-100 syringe pump (from Landgraf Laborsystem HLL GmbH) through a 10ml syringe with cannula, starting through an inlet in the front closing plate. For this purpose, a heating jacket is placed around the syringe and heated to 70 ℃ in order to keep the diisocyanate 1 liquid. The amount was metered continuously over exactly 1 hour, with timing starting from the start of metering. After 37 minutes, the viscosity in the extruder began to rise slowly. Can be identified by the force measured by the extruder (initially 95N). After 55 minutes, the external temperature was raised to 190 ℃. At this time, the extruder exhibited a force of 2900N. As the temperature increases, the force initially drops, but then rises again. After 5 minutes, the temperature was raised to an external temperature of 220 ℃; the force at this time was 4500N. After 60 minutes, the metering of diisocyanate 1 is ended. After the end of the metering, the viscosity in the extruder rose further, so that after 2 minutes the temperature rose to 235 ℃. The force is now 10500N. Within 20 minutes after the reaction, the viscosity and hence the force still further increased to 14000N. After 80 minutes, the polymer melt of the resulting thermoplastic polymer (polyoxazolidone) was removed as a polymer extrudate through a discharge valve.

2.2 comparative example 1: reaction of bisphenol A diglycidyl ether with MDI without a temperature gradient during the addition of MDI

In a nitrogen box, 60g of diepoxide 1 and 0.084g of catalyst 1 were weighed into a 100ml glass vessel equipped with a magnetic stir bar and sealed. The mixture was removed from the nitrogen box and mixed on a magnetic stirrer at 80 ℃ for 3 hours.

Both extruder screws were inserted into a 15ml twin screw MC 15 high torque and high force mini blender from xpore and closed firmly with a torque wrench (50 Nm). Heating to an external temperature of 100 ℃ is then carried out. Screw 2 closure plates onto the extruder. The rear panel has a joint for argon inerting. The front panel has an inlet for metering isocyanate.

A50 ml bottle containing diisocyanate 1 was melted in a drying oven at 70 ℃ for 1 hour.

12.2g of a warm mixture of diepoxide 1 and catalyst 1 are introduced into the extruder by briefly removing the front closing plate and heated to 100 ℃. After introduction, the insulation panels were reinstalled and the stirrer was started at 100 rpm. For inertization, the test specimen was covered with 20l/h of argon 4.6 from a gas cylinder. The temperature was raised from 100 ℃ to an external temperature of 180 ℃. The internal temperature was adjusted to 175 ℃ for 5 minutes. After this 5 minutes, 6.91ml of diisocyanate 1 were metered in using a LA-100 syringe pump (from Landgraf Laborsystem HLL GmbH) through a 10ml syringe with cannula, starting through an inlet in the front closing plate. For this purpose, a heating jacket is placed around the syringe and heated to 70 ℃ in order to keep the diisocyanate 1 liquid. The amount was metered continuously over exactly 1 hour, with timing starting from the start of metering.

After 42 minutes, the viscosity in the extruder began to rise very slowly. Can be identified by the force measured by the extruder (initially 88N). After 60 minutes, the metering of diisocyanate 1 is ended. The viscosity at this time was only 425N. After the end of the metering, the viscosity in the extruder rose further, so that after 15 minutes the temperature rose to 200 ℃. The force is now 4100N. After a further 5 minutes, the force was 7200N. After 80 minutes of operation, the polymer melt of the resulting thermoplastic polymer (polyoxazolidone) was removed as a polymer extrudate through a discharge valve.

2.3 example 2: reaction of bisphenol A diglycidyl ether with TDI with a temperature gradient during the addition of TDI

In a nitrogen box, 60g of diepoxide 1 and 0.084g of catalyst 1 were weighed into a 100ml glass vessel equipped with a magnetic stir bar and sealed. The mixture was removed from the nitrogen box and mixed on a magnetic stirrer at 80 ℃ for 3 hours.

Both extruder screws were inserted into a 15ml twin screw MC 15 high torque and high force mini blender from xpore and closed firmly with a torque wrench (50 Nm). Heating to an external temperature of 100 ℃ is then carried out. Screw 2 closure plates onto the extruder. The rear panel has a joint for argon inerting. The front panel has an inlet for metering isocyanate.

By briefly removing the front closure plate, exactly 13.9g of a warm mixture of diepoxide 1 and catalyst 1 are introduced into the extruder and heated to 100 ℃. The insulation panels were reinstalled and the stirrer was started at 100 rpm. For inertization, the test specimen was covered with 20l/h of argon 4.6 from a gas cylinder. The temperature was raised from 100 ℃ to an external temperature of 160 ℃. The internal temperature was adjusted to 155 ℃ for 5 minutes. After this 5 minutes, 5.77ml of diisocyanate 2 were metered in using a LA-100 syringe pump (from Landgraf Laborsystem HLL GmbH) through a 10ml syringe with cannula, starting through an inlet in the front closing plate. The amount was metered continuously over exactly 1 hour, with timing starting from the start of metering. After 35 minutes, the viscosity in the extruder began to rise slowly. Can be identified by the force measured by the extruder (initially 88N). After 50 minutes, the external temperature was raised to 190 ℃. At this time, the extruder exhibited a force of 3300N. As the temperature increases, the force initially drops, but then rises again. After 5 minutes, the temperature was raised to an external temperature of 210 ℃ and the extruder showed a force of 5900N. After a further 3 minutes, the external temperature was raised to 230 ℃. The extruder now shows a force of 7800N. After 60 minutes, the metering of diisocyanate 2 is ended. The viscosity in the extruder is now very high, which can be identified by a force of 10700N. Within 20 minutes after the reaction, the viscosity and hence the force increased still slightly further, to 13000N. After 80 minutes, the polymer melt of the resulting thermoplastic polymer (polyoxazolidone) was removed as a polymer extrudate through a discharge valve.

2.4 comparative example 2: (isothermal) reaction of bisphenol A diglycidyl ether with TDI without temperature gradients during the addition of TDI

In a nitrogen box, 60g of diepoxide 1 and 0.084g of catalyst 1 were weighed into a 100ml glass vessel equipped with a magnetic stir bar and sealed. The mixture was removed from the nitrogen box and mixed on a magnetic stirrer at 80 ℃ for 3 hours.

Both extruder screws were inserted into a 15ml twin screw MC 15 high torque and high force mini blender from xpore and closed firmly with a torque wrench (50 Nm). Heating to an external temperature of 100 ℃ is then carried out. 2 closing plates plus insulation plates were screwed onto the extruder. The rear panel has a joint for argon inerting. The front panel has an inlet for metering isocyanate.

By briefly removing the front closure plate, exactly 14.0g of a warm mixture of diepoxide 1 and catalyst 1 are introduced into the extruder and heated to 100 ℃. The sealing plate and insulating plate were reinstalled and the stirrer was started at 100 rpm. For inertization, the test specimen was covered with 20l/h of argon 4.6 from a gas cylinder. The temperature was raised from 100 ℃ to an external temperature of 160 ℃. The internal temperature was adjusted to 155 ℃ for 5 minutes. After this 5 minutes, 5.77ml of diisocyanate 2 were metered in using a LA-100 syringe pump (from Landgraf Laborsystem HLL GmbH) through a 10ml syringe with cannula, starting through an inlet in the front closing plate. The amount was metered continuously over exactly 1 hour, with timing starting from the start of metering. After 35 minutes, the viscosity in the extruder began to rise slowly. Can be identified by the force measured by the extruder (initially 60N). After 60 minutes, the metering of diisocyanate 2 is ended. The viscosity in the extruder is now very high, which can be identified by a force of 14742N. The product was discharged through a discharge valve and removed as a polymer extrudate with a rough surface and not completely transparent.

2.5 analysis

The resulting polymers of examples 1 and 2 and comparative examples 1,2 and 3 were subjected to various analyses as described below.

Solubility in water

The solubility test was performed in solvent 1: 0.25g of the polymer was dissolved in 4.75g of solvent 1. The mixture was stirred on a magnetic stirrer at 80 ℃ for 2 hours.

Molar mass distribution/GPC

The molar mass distribution of each polymer was determined using GPC (gel permeation chromatography). 0.2g of polymer was dissolved in 8ml of N, N-dimethylacetamide (99.8%) at room temperatureOvernight. The following day, 100. mu.l was injected into GPC via a 45 μm filter from Sartorius. Four 60cm Phenogel from Phenomenex at 0.7ml/min using an HPLC pump 0202 from Duratec on an RI2000 differential refractive index Detector from Duratec using N, N-dimethylacetamide as the eluent^TM5 μm chromatography columnThe detection is carried out. The measurement lasted 130 minutes. Polymethyl methacrylate was used as a control substance.

Weight average molar mass M of each polymer_wNumber average molar mass M_nIn each case determined by the values obtained. Furthermore, by forming the weight-average molar mass M of the individual thermoplastic polymers_wWith number average molar mass M_nTo determine the polydispersity PI: PI ═ M_w/M_n。

The results are given in table 1, in which the amounts of the reactants diepoxide 1 and the corresponding diisocyanate 1 or 2 are indicated, based on 100g diepoxide.

TABLE 1

Properties of the formulations and of the polymers obtained

Continuation 1 of Table 1

Continuation 2 of Table 1

Comparison between the examples and comparative examples clearly demonstrates that higher molecular weights (M) can be prepared by the selected method using a temperature gradient_nAnd M_wBoth) and lower polydispersityThe polymer of (1).

Cited documents

-DE 10 2014 226 838 A1

-WO 2015/173111 A1

-WO 2015/173110 A1、US 2014/0121299

-WO 2014/076024 A1

-PCT/EP2018/053612

-DE 102 02 838 A1

Angew. chem.2000,112, pages 3926-