A low-density aging-resistant fiber and preparation method thereof

Abstract

The present invention provides a low-density aging-resistant fiber and a preparation method thereof; the preparation method comprises the following steps: a) after mixing a high molecular weight diol and a low molecular weight polyol, adding isocyanate to carry out a first reaction, then adding a first solvent to dissolve and cooling, adding a mixture of a chain extender, a terminator and a second solvent, and sequentially carrying out a second reaction, a third reaction and aging to obtain a reaction mixture; b) adding an anti-aging agent and glass microbeads to the reaction mixture, stirring evenly and spinning to obtain a low-density aging-resistant fiber; the anti-aging agent is trihydroxymethylpropane triglycidyl ether. The preparation method provided by the present invention selects specific raw materials, especially introduces a small molecule anti-aging agent containing polyepoxy and glass microbeads, and cooperates with a specific preparation process to achieve overall good interaction, and the obtained low-density aging-resistant fiber has excellent aging resistance and low density on the basis of good and stable various properties.

Description

Technical Field

[0001] The invention relates to the technical field of fiber manufacturing, and more specifically to a low-density aging-resistant fiber and a preparation method thereof. Background Art

[0002] Polyurethane fiber is a common fiber with the advantages of good elasticity and high strength, and is widely used in daily life. However, since polyurethane fiber is synthesized from isocyanate and polyether, its aging resistance is relatively poor, and some use occasions have certain requirements for the density of polyurethane fiber. At present, the existing technology generally adopts the method of adding anti-aging agents to improve, but the effect is general and cannot meet the low density requirements of the product. Summary of the invention

[0003] In view of this, the object of the present invention is to provide a low-density aging-resistant fiber and a preparation method thereof. The low-density aging-resistant fiber provided by the present invention has excellent aging-resistant performance and low density on the basis of good and stable performance.

[0004] The present invention provides a method for preparing low-density aging-resistant fiber, comprising the following steps:

[0005] a) mixing a high molecular weight diol and a low molecular weight polyol, adding isocyanate to carry out a first reaction, then adding a first solvent to dissolve and cooling, adding a mixture of a chain extender, a terminator and a second solvent, and sequentially carrying out a second reaction, a third reaction and aging to obtain a reaction mixture;

[0006] b) adding an anti-aging agent and glass micro beads to the above reaction mixture, stirring evenly and spinning to obtain low-density aging-resistant fibers; the anti-aging agent is trihydroxymethylpropane triglycidyl ether.

[0007] Preferably, the high molecular weight diol in step a) is selected from one or more of polytetrahydrofuran diol, polyethylene glycol, polypropylene glycol, and polybutylene adipate diol; and the number average molecular weight of the high molecular weight diol is 1000 to 5000.

[0008] Preferably, the low molecular weight polyol in step a) is selected from one or more of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, and trimethylolpropane.

[0009] Preferably, the mixing process in step a) is specifically as follows:

[0010] The high molecular weight diol and the low molecular weight polyol are stirred and dehydrated at 80°C to 120°C, below -0.095 MPa, and 30 r / min to 80 r / min for 2h to 3h.

[0011] Preferably, the isocyanate in step a) is selected from one or more of HDI, IPDI, MDI and TDI;

[0012] The molar ratio of the isocyanate to the high molecular weight diol, the low molecular weight polyol, the chain extender and the terminator is 100:(50-95):(5-15):(2-8):(0.5-2).

[0013] Preferably, the first reaction in step a) is carried out in a nitrogen atmosphere at a temperature of 75° C. to 85° C. for 2 h to 3 h.

[0014] Preferably, the amount of the first solvent added in step a) is 50% to 200% of the total mass of the high molecular weight diol, the low molecular weight polyol and the isocyanate; the first solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide;

[0015] The dissolution speed is 30r / min to 80r / min, and the dissolution time is 0.3h to 0.6h;

[0016] The cooling temperature is 30°C to 40°C.

[0017] Preferably, the amount of the second solvent in step a) is 100% to 200% of the total mass of the chain extender and the terminator; the second solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide;

[0018] The chain extender is selected from one or more of ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, and 1,5-pentanediamine;

[0019] The terminator is selected from one or more of di-n-butylamine, tert-butylamine, n-butylamine and diethylamine.

[0020] Preferably, the temperature of the second reaction in step a) is 30°C to 40°C, and the time is 20min to 60min;

[0021] The temperature of the third reaction is 70°C to 85°C, and the time is 1h to 2h;

[0022] The aging temperature is 30° C. to 40° C., and the aging time is 24 h to 48 h.

[0023] Preferably, the true density of the glass microspheres in step b) is 0.2 to 0.7 g / cm 3 , D90 is 15~40μm;

[0024] The mass ratio of the solid content (excluding solvent), anti-aging agent and glass microbeads in the reaction mixture is 100:(0.3-1):(3-30);

[0025] The stirring time is 5 min to 10 min.

[0026] The present invention also provides a low-density aging-resistant fiber, which is prepared by the preparation method described in the above technical solution.

[0027] The present invention provides a low-density aging-resistant fiber and a preparation method thereof; the preparation method comprises the following steps: a) after mixing a high molecular weight diol and a low molecular weight polyol, adding isocyanate to carry out a first reaction, then adding a first solvent to dissolve and cooling, adding a mixture of a chain extender, a terminator and a second solvent, and sequentially carrying out a second reaction, a third reaction and aging to obtain a reaction mixture; b) adding an anti-aging agent and glass microbeads to the reaction mixture, stirring evenly and spinning to obtain a low-density aging-resistant fiber; the anti-aging agent is trihydroxymethylpropane triglycidyl ether. Compared with the prior art, the preparation method provided by the present invention selects specific raw materials, especially introduces a small molecule anti-aging agent containing polyepoxy and glass microbeads, cooperates with a specific preparation process, and achieves overall good interaction, and the obtained low-density aging-resistant fiber has excellent aging resistance and low density on the basis of good and stable performance.

[0028] At the same time, the preparation method provided by the present invention has simple process, mild conditions, easy control, and broad application prospects. DETAILED DESCRIPTION

[0029] The technical solution of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] The present invention provides a method for preparing low-density aging-resistant fiber, comprising the following steps:

[0031] a) mixing a high molecular weight diol and a low molecular weight polyol, adding isocyanate to carry out a first reaction, then adding a first solvent to dissolve and cooling, adding a mixture of a chain extender, a terminator and a second solvent, and sequentially carrying out a second reaction, a third reaction and aging to obtain a reaction mixture;

[0032] b) adding an anti-aging agent and glass micro beads to the above reaction mixture, stirring evenly and spinning to obtain low-density aging-resistant fibers; the anti-aging agent is trihydroxymethylpropane triglycidyl ether.

[0033] The invention firstly mixes a high molecular weight diol and a low molecular weight polyol, then adds isocyanate to carry out a first reaction, then adds a first solvent to dissolve and cools, then adds a mixture of a chain extender, a terminator and a second solvent, and sequentially carries out a second reaction, a third reaction and aging to obtain a reaction mixture.

[0034] In the present invention, the high molecular weight diol is preferably selected from one or more of polytetrahydrofuran diol, polyethylene glycol, polypropylene glycol, polybutylene adipate diol, more preferably polytetrahydrofuran diol, polyethylene glycol or polypropylene glycol; the number average molecular weight of the high molecular weight diol is preferably 1000 to 5000, more preferably 4500 to 5000. The present invention has no particular restrictions on the source of the high molecular weight diol, and commercially available products well known to those skilled in the art can be used.

[0035] In the present invention, the number of carbon atoms of the low molecular weight polyol is preferably 2 to 10. In the present invention, the low molecular weight polyol is preferably selected from one or more of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, trimethylolpropane, more preferably two of diethylene glycol, triethylene glycol, trimethylolpropane; in a preferred embodiment of the present invention, the low molecular weight polyol is trimethylolpropane and diethylene glycol in a molar ratio of 2:13; or, trimethylolpropane and triethylene glycol in a molar ratio of 2:13; or, trimethylolpropane and triethylene glycol in a molar ratio of 3:10. The present invention has no special restrictions on the source of the low molecular weight polyol, and commercially available products well known to those skilled in the art can be used.

[0036] In the present invention, the mixing process is preferably specifically as follows:

[0037] The high molecular weight diol and the low molecular weight polyol are stirred and dehydrated at 80°C to 120°C, below -0.095 MPa, and 30 r / min to 80 r / min for 2h to 3h.

[0038] In the present invention, the isocyanate is preferably selected from one or more of HDI, IPDI, MDI, and TDI, and more preferably MDI or TDI. The present invention has no particular limitation on the source of the isocyanate, and commercial products known to those skilled in the art can be used.

[0039] In the present invention, the molar ratio of the isocyanate to the high molecular weight diol, the low molecular weight polyol, the chain extender and the terminator is preferably 100:(50-95):(5-15):(2-8):(0.5-2), and more preferably 100:(80-82):(13-15):(3-3.5):(1-1.6).

[0040] In the present invention, the first reaction is preferably carried out in a nitrogen atmosphere, the temperature is preferably 75° C. to 85° C., and the time is preferably 2 h to 3 h.

[0041] In the present invention, the amount of the first solvent added is preferably 50% to 200% of the total mass of the high molecular weight diol, the low molecular weight polyol and the isocyanate, and more preferably 80% to 120%.

[0042] In the present invention, the first solvent is preferably selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, and more preferably N,N-dimethylformamide or N,N-dimethylacetamide. The present invention has no particular limitation on the source of the first solvent, and commercially available products known to those skilled in the art can be used.

[0043] In the present invention, the dissolution speed is preferably 30 r / min to 80 r / min, and the dissolution time is preferably 0.3 h to 0.6 h.

[0044] In the present invention, the cooling temperature is preferably 30°C to 40°C.

[0045] In the present invention, the amount of the second solvent is preferably 100% to 200% of the total mass of the chain extender and the terminator, and more preferably 100% to 150%.

[0046] In the present invention, the second solvent is preferably selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide, and more preferably N,N-dimethylformamide or N,N-dimethylacetamide. The present invention has no particular limitation on the source of the second solvent, and commercially available products known to those skilled in the art can be used.

[0047] In the present invention, the chain extender is preferably selected from one or more of ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, and 1,5-pentanediamine, and more preferably 1,3-propylenediamine, 1,4-butylenediamine, or 1,5-pentanediamine. The present invention has no particular limitation on the source of the chain extender, and commercially available products known to those skilled in the art can be used.

[0048] In the present invention, the terminator is preferably selected from one or more of di-n-butylamine, tert-butylamine, n-butylamine, and diethylamine, and more preferably n-butylamine, tert-butylamine, or diethylamine. The present invention has no particular limitation on the source of the chain extender, and commercially available products of the above-mentioned monofunctional amines well known to those skilled in the art can be used.

[0049] In the present invention, the temperature of the second reaction is preferably 30°C to 40°C, and the time is preferably 20min to 60min;

[0050] In the present invention, the temperature of the third reaction is preferably 70°C to 85°C, and the time is preferably 1h to 2h;

[0051] In the present invention, the aging temperature is preferably 30° C. to 40° C., and the aging time is preferably 24 h to 48 h.

[0052] After obtaining the reaction mixture, the present invention adds an anti-aging agent and glass microbeads to the reaction mixture, stirs evenly and then spins to obtain low-density anti-aging fibers.

[0053] In the present invention, the anti-aging agent is trimethylolpropane triglycidyl ether. The present invention has no special restrictions on the source of the anti-aging agent, and commercial products well known to those skilled in the art can be used.

[0054] In the present invention, the true density of the glass microspheres is preferably 0.2 to 0.7 g / cm 3 , D90 is preferably 15-40 μm. The present invention has no special restrictions on the source of the glass microspheres, and commercial products known to those skilled in the art can be used. In the present invention, glass microspheres have the characteristics of low density and high strength, and are widely used in adhesives, coatings, plastic modification, etc. to reduce density and improve thermal insulation performance.

[0055] In the present invention, since the reaction mixture contains carbamate groups, which react with epoxy groups under certain conditions, by introducing polyepoxy-containing small molecules and glass microbeads during the fiber synthesis process, an aging-resistant and lightweight fiber product can be prepared.

[0056] In the present invention, the mass ratio of the solid content (excluding solvent), anti-aging agent and glass microbeads in the reaction mixture is preferably 100:(0.3-1):(3-30), more preferably 100:(0.5-0.6):(4-6).

[0057] In the present invention, the stirring time is preferably 5 min to 10 min.

[0058] The present invention also provides a low-density aging-resistant fiber, which is prepared by the preparation method described in the above technical solution. In the present invention, the preparation method introduces new substances (small molecules containing polyepoxy and glass microbeads) in the process of synthesizing polyurethane fibers, so that the synthesized fibers have the characteristics of aging resistance and light weight.

[0059] The present invention provides a low-density aging-resistant fiber and a preparation method thereof; the preparation method comprises the following steps: a) after mixing a high molecular weight diol and a low molecular weight polyol, adding isocyanate to carry out a first reaction, then adding a first solvent to dissolve and cooling, adding a mixture of a chain extender, a terminator and a second solvent, and sequentially carrying out a second reaction, a third reaction and aging to obtain a reaction mixture; b) adding an anti-aging agent and glass microbeads to the reaction mixture, stirring evenly and spinning to obtain a low-density aging-resistant fiber; the anti-aging agent is trihydroxymethylpropane triglycidyl ether. Compared with the prior art, the preparation method provided by the present invention selects specific raw materials, especially introduces a small molecule anti-aging agent containing polyepoxy and glass microbeads, cooperates with a specific preparation process, and achieves overall good interaction, and the obtained low-density aging-resistant fiber has excellent aging resistance and low density on the basis of good and stable performance.

[0060] At the same time, the preparation method provided by the present invention has simple process, mild conditions, easy control, and broad application prospects.

[0061] In order to further illustrate the present invention, the following examples are used to explain it in detail. The raw materials used in the following examples and comparative examples of the present invention are all commercially available; among them, the glass microspheres used are produced by Saint-Laite Company with a true density of 0.2 to 0.7 g / cm 3 , hollow glass microspheres with D90 of 15 to 40 μm.

[0062] Example 1

[0063] (1) Ratio of reaction materials (prepared in molar ratio):

[0064] Isocyanate (MDI) 100 parts;

[0065] 81 parts of polytetrahydrofuran diol with a molecular weight of 5000;

[0066] 2 parts of trimethylolpropane;

[0067] 13 parts of diethylene glycol;

[0068] 3.5 parts of 1,3-propylenediamine;

[0069] 1 part of n-butylamine;

[0070] (2) The polytetrahydrofuran diol, trimethylolpropane and diethylene glycol with a molecular weight of 5000 are stirred and dehydrated at 100° C., below -0.095 MPa, and 55 r / min for 2.5 h; then isocyanate is added, and the reaction is carried out at 80° C. in a nitrogen atmosphere for 2.5 h; then N,N-dimethylformamide, a solvent accounting for 80% of the total mass of the above-mentioned reaction materials, is added, and the reaction is dissolved at a speed of 55 r / min for 0.5 h; then the temperature is lowered to 35° C., and chain extender 1,3-propylenediamine, terminator n-butylamine, and and a mixture of solvent N,N-dimethylformamide with a total weight of 100% of the chain extender and the terminator, react for 40 minutes after addition, then heat to 78°C and continue to react for 1.5 hours, and then mature at 35°C for 36 hours to obtain a reaction mixture; finally, add 0.5% of the solid weight of the above reaction mixture as an anti-aging agent trimethylolpropane triglycidyl ether and 4% of the solid weight of the above reaction mixture as glass microbeads (HS42), stir for 8 minutes and then spin into silk to obtain low-density aging-resistant fibers; the density is 0.94g / cm 3 .

[0071] Example 2

[0072] (1) Ratio of reaction materials (prepared in molar ratio):

[0073] Isocyanate (TDI) 100 parts;

[0074] 80 parts of polyethylene glycol with a molecular weight of 4500;

[0075] 2 parts of trimethylolpropane;

[0076] 13 parts of triethylene glycol;

[0077] 3.2 parts of 1,4-butanediamine;

[0078] 1.6 parts of tert-butylamine;

[0079] (2) The polyethylene glycol, trimethylolpropane and triethylene glycol with a molecular weight of 4500 are stirred and dehydrated at 100°C, below -0.095 MPa, and 55 r / min for 2.5 h; then isocyanate is added, and the reaction is carried out at 80°C in a nitrogen atmosphere for 2.5 h; then N,N-dimethylformamide, a solvent with a mass percentage of 120% of the total mass of the reaction materials, is added, and the mixture is dissolved at a speed of 55 r / min for 0.5 h; then the temperature is lowered to 35°C, and a chain extender 1,4-butanediamine, a terminator tert-butylamine, and A mixture of solvent N,N-dimethylformamide with a total weight of 150% of the chain extender and the terminator was added, and the reaction was continued for 40 minutes, and then the temperature was raised to 78°C for 1.5 hours, and then aged at 35°C for 36 hours to obtain a reaction mixture; finally, 0.6% of the solid weight of the reaction mixture was added with trimethylolpropane triglycidyl ether, an anti-aging agent, and 6% of the solid weight of the reaction mixture were added with glass microbeads (HS70), and the mixture was stirred for 8 minutes and spun into silk to obtain low-density aging-resistant fibers; the density was 0.96g / cm 3 .

[0080] Example 3

[0081] (1) Ratio of reaction materials (prepared in molar ratio):

[0082] Isocyanate (MDI) 100 parts;

[0083] 82 parts of polypropylene glycol with a molecular weight of 4800;

[0084] 3 parts of trimethylolpropane;

[0085] 10 parts of triethylene glycol;

[0086] 3 parts of 1,5-pentanediamine;

[0087] 1 part of diethylamine;

[0088] (2) The polypropylene glycol, trimethylolpropane and triethylene glycol with a molecular weight of 4800 are stirred and dehydrated at 100°C, below -0.095 MPa, and 55 r / min for 2.5 h; then isocyanate is added, and the reaction is carried out at 80°C in a nitrogen atmosphere for 2.5 h; then N,N-dimethylacetamide, a solvent with a mass percentage of 120% of the total mass of the reaction materials, is added, and the mixture is dissolved at a speed of 55 r / min for 0.5 h; then the temperature is lowered to 35°C, and a chain extender 1,5-pentanediamine, a terminator diethylamine, and A mixture of solvent N,N-dimethylacetamide with a total weight of 120% of the chain extender and the terminator was added, and the reaction was continued for 40 minutes, and then the temperature was raised to 78°C for 1.5 hours, and then aged at 35°C for 36 hours to obtain a reaction mixture; finally, 0.6% of the solid weight of the reaction mixture was added with trimethylolpropane triglycidyl ether, an anti-aging agent, and 5% of the solid weight of the reaction mixture were added with glass microbeads (HS60), and the mixture was stirred for 8 minutes and spun into silk to obtain low-density aging-resistant fibers; the density was 0.96g / cm 3 .

[0089] Comparative Example 1

[0090] The preparation method provided in Example 1 is adopted, except that the anti-aging agent trimethylolpropane triglycidyl ether is not added; and low-density fibers are obtained.

[0091] Comparative Example 2

[0092] The preparation method provided in Example 1 is adopted, except that: the antioxidant trimethylolpropane triglycidyl ether is not added, and an antioxidant 1098 of equal mass is used instead; and low-density fibers are obtained.

[0093] Comparative Example 3

[0094] The preparation method provided in Example 1 is adopted, except that: the antioxidant trimethylolpropane triglycidyl ether is not added, and an antioxidant 1010 of equal mass is used instead; and low-density fibers are obtained.

[0095] Performance test: Each embodiment and comparative example was spun into a fiber with a diameter of 0.25 mm, and the fiber with a length of 50 cm was used to test its breaking strength, elongation at break and stress when stretched 300%. It was cured for 5 days at 70°C and 95% relative humidity to test its performance; the results are shown in Table 1 below.

[0096] Table 1 Product performance data of each embodiment and comparative example

[0097]

[0098] It can be seen from Table 1 that the present invention, by selecting small molecules containing multiple epoxy functional groups as antioxidants, can more obviously demonstrate the anti-aging effect in terms of performance compared with traditional antioxidants (preventing the degradation of molecular chains).

[0099] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather to the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A method for preparing low-density aging-resistant fiber, comprising the following steps: a) mixing a high molecular weight diol and a low molecular weight polyol, adding isocyanate to carry out a first reaction, then adding a first solvent to dissolve and cooling, adding a mixture of a chain extender, a terminator and a second solvent, and sequentially carrying out a second reaction, a third reaction and aging to obtain a reaction mixture; the high molecular weight diol is selected from one or more of polytetrahydrofuran diol, polyethylene glycol, polypropylene glycol, and polybutylene adipate diol; and the number average molecular weight of the high molecular weight diol is 1000-5000; The low molecular weight polyol is selected from one or more of ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, triethylene glycol, and trimethylolpropane; The mixing process is specifically as follows: Stir and dehydrate the high molecular weight diol and the low molecular weight polyol at 80°C to 120°C, below -0.095MPa, and 30r / min to 80r / min for 2h to 3h; b) adding an anti-aging agent and glass micro-beads to the above reaction mixture, stirring evenly and spinning to obtain low-density anti-aging fibers; the anti-aging agent is trihydroxymethylpropane triglycidyl ether; the true density of the glass micro-beads is 0.2-0.7 g / cm 3 , D90 is 15~40μm; The mass ratio of the solid content, anti-aging agent and glass microbeads in the reaction mixture is 100:(0.3-1):(3-30); The stirring time is 5 min to 10 min.

2. The preparation method according to claim 1, characterized in that: The isocyanate in step a) is selected from one or more of HDI, IPDI, MDI and TDI; The molar ratio of the isocyanate to the high molecular weight diol, the low molecular weight polyol, the chain extender and the terminator is 100:(50-95):(5-15):(2-8):(0.5-2).

3. The preparation method according to claim 1, characterized in that: The first reaction in step a) is carried out in a nitrogen atmosphere at a temperature of 75° C. to 85° C. for 2 h to 3 h.

4. The preparation method according to claim 1, characterized in that: The amount of the first solvent added in step a) is 50% to 200% of the total mass of the high molecular weight diol, the low molecular weight polyol and the isocyanate; the first solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide and dimethyl sulfoxide; The dissolution speed is 30r / min to 80r / min, and the dissolution time is 0.3h to 0.6h; The cooling temperature is 30°C to 40°C.

5. The preparation method according to claim 1, characterized in that: In step a), the amount of the second solvent is 100% to 200% of the total mass of the chain extender and the terminator; the second solvent is selected from one or more of N,N-dimethylformamide, N,N-dimethylacetamide, and dimethyl sulfoxide; The chain extender is selected from one or more of ethylenediamine, 1,3-propylenediamine, 1,4-butylenediamine, and 1,5-pentanediamine; The terminator is selected from one or more of di-n-butylamine, tert-butylamine, n-butylamine and diethylamine.

6. The preparation method according to claim 1, characterized in that: The temperature of the second reaction in step a) is 30°C to 40°C, and the time is 20min to 60min; The temperature of the third reaction is 70°C to 85°C, and the time is 1h to 2h; The aging temperature is 30° C. to 40° C., and the aging time is 24 h to 48 h.

7. A low-density aging-resistant fiber, characterized in that: The preparation method is described in any one of claims 1 to 6.

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