CN102382301B - Melt-spinnable spandex resin and production method thereof - Google Patents
Melt-spinnable spandex resin and production method thereof Download PDFInfo
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Abstract
The invention discloses a melt-spinnable spandex resin and a production method thereof, which belong to the fields of material chemistry and polymer synthesis. The invention prepares the melt-spinnable spandex resin material with terephthalic acid, ursol and terephthalic acid block polymer as rigid groups and polyoxyethylene or polyoxypropylene with different chain segment lengths as a flexible chain segment, spandex resin materials with different melting temperatures and elongations can be obtained by modulating the structure and the length of the flexible chain segment, the glass-transition temperature of the obtained material is lower than 60 DEG C below zero, and the material is in a highly elastic state under the condition of normal temperature, and has good elastic recovery capability; and the melting temperature range of the obtained spandex resin is between 170 DEG C and 208 DEG C, the thermal decomposition temperature of the material in the air reaches more than 400 DEG C, and the spandex resin has excellent melt-spinning properties.
Description
Technical field:
The present invention relates to materials chemistry and Polymer Synthesizing field, specially refer to a kind of rigidity that has, soft segment controlled the preparation method of spandex resin.
Technical background:
Recent years, along with the fast development of chemical industry and Clothing industry, filamentary material has obtained increasing extensively attention, and wherein synthon have shown potential using value as the heaviest textile raw material.In numerous composite fibre materials, spandex (also claiming spandex fiber) is one of synthon of being most widely used of a class.Spandex generally is divided into two kinds: the two different propylhomoserin enzymes of fragrance and the block copolymer that contains the polyester segment of hydroxyl (being called for short the polyester type spandex), another kind are by the two isocyanic ester of fragrance and the polyether segment block copolymer that contains hydroxyl (abbreviation polyether-type spandex).It is a kind of material best in synthon that spandex has high extension at break (more than 400%), low modulus and high elastic recovery rate and extensibility (4-8 of itself doubly) with it; This material has tensile elasticity and recovery characteristic, resistance to acids and bases, solvent resistance, wear resistance, dyeability, thermotolerance and resistance to deterioration preferably simultaneously, makes it have using value very widely in fields such as knitting socks production, gloves, sweat shirt, swim suit, elastic tape, bandage, tights.
For spandex resin is widely used, spinning process be one very in important link, spining technology commonly used comprises at present: dry-spinning, wet-spinning, chemical method spinning and melt-spinning etc.; Wherein the method for scorification spinning is simple to equipment requirements, spinning is with low cost, has potential prospects for commercial application; But melt-spinning is only applicable to the meltable polymkeric substance good with the melt temperature stability inferior, and this class spandex resin kind is not a lot, has limited it and has used widely.So the spandex resin material of developing novel melt-spinnable also is very important.
Summary of the invention:
A first aspect of the present invention is to provide a kind of spandex resin of melt-spinnable, its structural formula as shown in Equation 1:
Formula 1.
In formula 1: TPT is the rigid chain segment of terephthalic acid, Ursol D, terephthalic acid block polymer composition, and PEO is the polyoxyethylene soft segment.
A kind of spandex resin of melt-spinnable, its structural formula be as shown in Equation 2:
Formula 2.
In formula 2: TPT is the rigid chain segment of terephthalic acid, Ursol D, terephthalic acid block polymer composition, and " PPO " is the polyoxypropylene soft segment.
Spandex resin of the present invention, by using poly terephthalic acid, Ursol D, Ursol D segmented copolymer as the rigid chain segment of spandex resin, adopting polyoxyethylene or polyoxypropylene is soft segment, spandex resin of the present invention and conventional spandex resin-phase are relatively, has very low melt temperature, overcome the shortcomings such as the high material breakdown that causes of traditional spinning melt temperature, equipment holding capacity be large, and had good elasticity response rate, extensibility, its characteristic is as follows:
1, spandex resin of the present invention: be in elastomeric state under normal temperature, second-order transition temperature has excellent melt-spinning performance all lower than-60 ℃, and melt temperature is conducive to large-scale melt-spun at 170-208 ℃, reduces the spinning cost of material; And resulting novel spandex resin has excellent thermostability, and the heat decomposition temperature under air conditions can reach more than 400 ℃.
2, spandex resin of the present invention: have excellent extensibility, the tensile modulus of normal temperature material is 2.6GP, and the maximum elongation degree reaches 10 times, and corresponding temperature is 30 ℃, can increase the flexibility that north agent (as n-butyl phthalate, dimethyl phthalate) increases material by interpolation.And after type becomes, material has good rebound resilience (near 100%), is better than the spandex fibre that a lot of business are used; The excellent flexible and mechanical property preferably of resulting spandex resin simultaneously.
A second aspect of the present invention is to provide a kind of preparation method of spandex resin of above-mentioned melt-spinnable, comprises the following steps:
1, synthetic TPT reactive monomer: with terephthalic acid and Ursol D polymerization, then pass through decyl alcohol or methyl alcohol functional modification, obtain the TPT reactive monomer;
Further: polymerization temperature is preferably 150～160 ℃, and polyreaction adopts melt polymerization, and perhaps polyreaction adopts the normal pressure solution polymerization, and solvent is selected DMAC, DMF, DMSO or nmp solvent.
Utilize aforesaid method to synthesize the TPT-dimethyl reactive monomer: 100 gram terephthalic acids are dissolved in 500 milliliters of DMF solvents; Simultaneously 15 gram Ursol D are dissolved in 200 milliliters of DMF, then slowly join in terephthaldehyde's acid solution, stirring adds 250 ml methanol after half an hour, the temperature of reaction to 150 that raises simultaneously ℃, after 15 minutes, product is cooling, toluene wash, washing with acetone, 70 ℃ of dried overnight.
Utilize aforesaid method to synthesize the TPT-didecanyl reactive monomer: 100 gram terephthalic acids are dissolved in 500 milliliters of DMF solvents; Simultaneously 15 gram Ursol D are dissolved in 200 milliliters of DMF, then slowly join in terephthaldehyde's acid solution, stirring adds 250 milliliters of decyl alcohol after half an hour, the temperature of reaction to 75 that raises simultaneously ℃, the reaction times is 4 hours, product is cooling, toluene wash, washing with acetone, 70 ℃ of dried overnight.
2, utilize above-mentioned synthetic TPT reactive monomer and polyoxyethylene (PEO) or polyoxypropylene (PPO) polymerization of different molecular weight, can obtain the spandex resin of melt-spinnable of the present invention.
According to aforesaid method of the present invention, TPT-PEO or the TPT-PPO spandex resin that can prepare the hard and soft segment of different chain lengths, be in TPT-PEO of the present invention or TPT-PPO spandex resin just, soft segment is controlled, wherein: but quality percentage composition modulation between 3.4-23wt% of TPT rigid chain segment; Soft segment is chosen as PEO segment or PPO segment, but the length of soft segment modulation between 600-3600, and the segment ratio modulation of above-mentioned TPT-PEO or TPT-PPO is regulated and can be completed when reinforced.
Further: the polyreaction of step 2 is preferably at 180 ℃～250 ℃ temperature, under the nitrogen protection condition, carries out under take isopropyl titanate m-xylene solution as catalyzer.
By the synthetic TPT-PEO of TPT-dimethyl reactive monomer: synthesize under the nitrogen protection condition, with carrying out in the reactor of mechanical stirring function, 4.32 gram TPT-dimethyl reactive monomers, 10 gram PEO
600Monomer is warmed up to 180 ℃, and the isopropyl titanate m-xylene solution of 1 milliliter of 0.05M adds in reaction system as the catalyzer of reaction, and after 30 minutes, reaction is warmed up to 220 ℃, keeps finishing in two hours, slowly cools to room temperature, filters and namely obtains target product.
By the synthetic TPT-PEO of TPT-didecanyl reactive monomer.Synthesize under the nitrogen protection condition, with carrying out in the reactor of mechanical stirring function, 6.84 gram TPT-didecanyl reactive monomers, 10 gram PEO
3600Monomer, the isopropyl titanate m-xylene solution of 1 milliliter of 0.05M adds in reaction system as the catalyzer of reaction, 275 ℃ of extrusion reactions in airtight reactor, then adding the isopropyl titanate m-xylene solution of 1 milliliter of 0.05M, 250 ℃ were reacted 2 hours, slowly be depressurized to normal pressure, cool at last room temperature, obtain target product.
By the synthetic TPT-PPO of TPT-dimethyl reactive monomer.Synthesize under the nitrogen protection condition, with carrying out in the reactor of mechanical stirring function, 4.32 gram TPT-dimethyl reactive monomers, 10 gram PPO
2000Monomer is warmed up to 150 ℃, and the isopropyl titanate m-xylene solution of 1 milliliter of 0.05M adds in reaction system as the catalyzer of reaction, and after 30 minutes, reaction is warmed up to 230 ℃, keeps finishing in two hours, slowly cools to room temperature, filters and namely obtains target product.
spandex resin of the present invention, can be applied to the production of spandex fibre, adopting conventional melt-spinning technology is the excellent spandex fibre of availability energy, for further improving the melt-spinning performance of spandex resin of the present invention, can introduce different auxiliary agent n-butyl phthalates in the process of spinning, dimethyl phthalate, can effectively increase the flexibility of spandex, reduce spinning temperature, increase the elongation (reaching 12 times of left and right) of spandex and the fracture probability of finished silk, improve the service efficiency of material, its impact of performance is much better than the business spandex resin.
Beneficial effect of the present invention is as follows:
1, the preparation method is simply effective: utilize the method for simple solution polymerization to obtain the novel spandex resin of different segment ratios, and with low cost.
2, the novel spandex resin of the present invention's preparation at room temperature has excellent extensibility and elastic recovery rate.
3, the novel spandex resin of the present invention's preparation has lower melt temperature, is conducive to spinning under the material melting condition, reduces the requirement to equipment.
4, the novel spandex resin of the present invention's preparation has excellent thermostability, reaches more than 400 ℃.
5, the maximum extensibility of the room temperature of the novel spandex resin of the present invention's preparation reaches 10 times of left and right, is better than the spandex resin material that a lot of business are used, and has very strong application prospect; Add the extensibility that increases the later material of north agent (n-butyl phthalate, dimethyl phthalate) and can reach 12 times, and kept good elastic recovery rate.
6, the room temperature tensile modulus of the novel spandex resin of the present invention's preparation more than 2.6GP, has excellent stretch-proof ability, prevents the brittle rupture of material in drawing process.
Below in conjunction with embodiment, the invention will be further described.
Description of drawings:
Fig. 1 is embodiment of the present invention TPT-PEO
800The differential thermal thermogravimetric curve figure of material;
Fig. 2 is embodiment of the present invention TPT-PEO
800The nuclear magnetic spectrum analysis of material.
Embodiment:
In following embodiment, sample name is divided into two portions: TPT and represents terephthalic acid, Ursol D, terephthalic acid block polymer rigid chain segment, " PEO " polyoxyethylene or " PPO " polyoxypropylene is soft segment.
Embodiment 1:
At first synthetic TPT-dimethyl reactive monomer: 100 gram terephthalic acids are dissolved in 500 milliliters of DMF solvents; 15 gram Ursol D are dissolved in 200 milliliters of DMF simultaneously, then slowly join (30 minutes) in terephthaldehyde's acid solution, add 250 ml methanol after stirring half an hour, the temperature of reaction to 150 that raises simultaneously ℃, after 15 minutes, product is cooling, toluene wash, washing with acetone, 70 ℃ of dried overnight.
By the synthetic TPT-PEO of TPT-dimethyl reactive monomer.Synthesize under the nitrogen protection condition, with carrying out in the reactor of mechanical stirring function, 4.32 gram TPT-dimethyl reactive monomers, 10 gram PEO
600Monomer is warmed up to 180 ℃, and the isopropyl titanate m-xylene solution of 1 milliliter of 0.05M adds in reaction system as the catalyzer of reaction, and after 30 minutes, reaction is warmed up to 220 ℃, keeps finishing in two hours.Slowly cool to room temperature, filter and namely obtain target product.
Embodiment 2:
At first synthetic TPT-didecanyl reactive monomer: 100 gram terephthalic acids are dissolved in 500 milliliters of DMF solvents; 15 gram Ursol D are dissolved in 200 milliliters of DMF simultaneously, then slowly join in terephthaldehyde's acid solution and (drip about 30 minutes), add 250 milliliters of decyl alcohol after stirring half an hour, the temperature of reaction to 75 that raises simultaneously ℃, reaction times is 4 hours, and product is cooling, toluene wash, washing with acetone, 70 ℃ of dried overnight.
By the synthetic TPT-PEO of TPT-didecanyl reactive monomer.Synthesize under the nitrogen protection condition, with carrying out in the reactor of mechanical stirring function, 6.84 gram TPT-didecanyl reactive monomers, 10 gram PEO
3600Monomer, the isopropyl titanate m-xylene solution of 1 milliliter of 0.05M adds in reaction system as the catalyzer of reaction, 275 ℃ of extrusion reactions in airtight reactor, then adding the isopropyl titanate m-xylene solution of 1 milliliter of 0.05M, 250 ℃ were reacted 2 hours, slowly be depressurized to normal pressure (approximately 1 hour), cool at last room temperature, obtain target product.
Embodiment 3:
At first synthetic TPT-dimethyl reactive monomer: 100 gram terephthalic acids are dissolved in 500 milliliters of DMF solvents; 15 gram Ursol D are dissolved in 200 milliliters of DMF simultaneously, then slowly join (30 minutes) in terephthaldehyde's acid solution, add 250 ml methanol after stirring half an hour, the temperature of reaction to 160 that raises simultaneously ℃, after 15 minutes, product is cooling, toluene wash, washing with acetone, 70 ℃ of dried overnight.
By the synthetic TPT-PPO of TPT-dimethyl reactive monomer.Synthesize under the nitrogen protection condition, with carrying out in the reactor of mechanical stirring function, 4.32 gram TPT-dimethyl reactive monomers, 10 gram PPO
2000Monomer is warmed up to 150 ℃, and the isopropyl titanate m-xylene solution of 1 milliliter of 0.05M adds in reaction system as the catalyzer of reaction, and after 30 minutes, reaction is warmed up to 230 ℃, keeps finishing in two hours.Slowly cool to room temperature, filter and namely obtain target product.
By adjusting the quality percentage composition of TPT rigid chain segment; And the length of soft segment, thereby the product that obtains different segment ratios is as shown in table 1, and table 1 has provided the segment ratio of different samples, the extensibility test of DMA data and material, the chain length of illustrative material is controlled, has extensibility and excellent tensile modulus values preferably.
The segment ratio of table 1, different samples, DMA data and correlated performance data.
Get above-mentioned TPT-PEO
800Specimen material, carry out differential thermal thermogravimetric analysis, Infrared spectroscopy, nuclear magnetic spectrum analysis, respectively as shown in Figure 1 and Figure 2.
Fig. 1 is TPT-PEO
800The differential thermal thermogravimetric curve of material, as seen from Figure 1: the aerial stability of material reaches 400 degree.TPT-PEO
800Material 1H NMR characterization result as shown in Figure 2.
To TPT-PEO
800Material carries out Infrared spectroscopy, determines the molecular structure of spandex resin, wherein: 3500-3200cm
-1Be the stretching vibration peak of NH2,3000-2800cm
-1Be the characteristic peak of methylene radical, 1730cm
-1Be the characteristic peak of carboxyl, 1100cm
-1Be the vibration peak of ether-oxygen bond, 1680cm
-1Characteristic peak for phenyl ring.
To sum up, the invention provides a kind of with low cost, have a spandex resin material hard and soft block of different ratios, melt-spinnable, reach design to spandex resin with synthetic by designing synthetic hard and soft property segment in synthetic process.by a series of detection analysis, comprise means of differential scanning calorimetry (DSC), the discoveries such as dynamic mechanical analysis (DMA), this material has excellent thermostability and lower melt temperature, proves that this material has excellent melt-spinning characteristic, flexibility test after spinning, stress-strain test finds out that finished product spandex filament resin has excellent elastic recovery, elongation and extension at break modulus, simultaneously in the process of spinning, can successful introducing increase north agent (dibutyl phthalate or dimethyl phthalate), after introducing increases north agent, in the thermostability that keeps the material excellence, reduced the melt temperature (157 ℃) of material, snappiness and the extensibility (12 times of left and right) of material have been increased simultaneously, overcome the shortcoming that a lot of conventional spandex materials are not suitable for melt-spinning, reduced the cost of spandex fiber process when keeping commodity spandex excellent properties, has significant technique effect.
Claims (2)
1. the preparation method of the spandex resin of a melt-spinnable is characterized in that:
(1), synthetic TPT-dimethyl reactive monomer: 100 gram terephthalic acids are dissolved in 500 milliliters of DMF solvents; Simultaneously 15 gram Ursol D are dissolved in 200 milliliters of DMF, then slowly join in terephthaldehyde's acid solution, stirring adds 250 ml methanol after half an hour, the temperature of reaction to 150 that raises simultaneously ℃, after 15 minutes, product is cooling, toluene wash, washing with acetone, 70 ℃ of dried overnight;
(2), by the synthetic TPT-PEO of TPT-dimethyl reactive monomer: synthesize under the nitrogen protection condition, with carrying out in the reactor of mechanical stirring function, 4.32 gram TPT-dimethyl reactive monomers, 10 gram PEO
600Monomer is warmed up to 180 ℃, and the isopropyl titanate m-xylene solution of 1 milliliter of 0.05M adds in reaction system as the catalyzer of reaction, and after 30 minutes, reaction is warmed up to 220 ℃, keeps finishing in two hours, slowly cools to room temperature, filters and namely obtains target product.
2. the preparation method of the spandex resin of a melt-spinnable is characterized in that:
(1), synthetic TPT-didecanyl reactive monomer: 100 gram terephthalic acids are dissolved in 500 milliliters of DMF solvents; Simultaneously 15 gram Ursol D are dissolved in 200 milliliters of DMF, then slowly join in terephthaldehyde's acid solution, stirring adds 250 milliliters of decyl alcohol after half an hour, the temperature of reaction to 75 that raises simultaneously ℃, the reaction times is 4 hours, product is cooling, toluene wash, washing with acetone, 70 ℃ of dried overnight;
(2), by the synthetic TPT-PEO of TPT-didecanyl reactive monomer: synthesize under the nitrogen protection condition, with carrying out in the reactor of mechanical stirring function, 6.84 gram TPT-didecanyl reactive monomers, 10 gram PEO
3600Monomer, the isopropyl titanate m-xylene solution of 1 milliliter of 0.05M adds in reaction system as the catalyzer of reaction, 275 ℃ of extrusion reactions in airtight reactor, and then add the isopropyl titanate m-xylene solution of 1 milliliter of 0.05M, 250 ℃ were reacted 2 hours, slowly be depressurized to normal pressure, cool at last room temperature, obtain target product.
3, a kind of preparation method of spandex resin of melt-spinnable is characterized in that:
(1), synthetic TPT-dimethyl reactive monomer: 100 gram terephthalic acids are dissolved in 500 milliliters of DMF solvents; Simultaneously 15 gram Ursol D are dissolved in 200 milliliters of DMF, then slowly join in terephthaldehyde's acid solution, stirring adds 250 ml methanol after half an hour, the temperature of reaction to 150 that raises simultaneously ℃, after 15 minutes, product is cooling, toluene wash, washing with acetone, 70 ℃ of dried overnight;
(2), by the synthetic TPT-PPO of TPT-dimethyl reactive monomer: synthesize under the nitrogen protection condition, with carrying out in the reactor of mechanical stirring function, 4.32 gram TPT-dimethyl reactive monomers, 10 gram PPO
2000Monomer is warmed up to 150 ℃, and the isopropyl titanate m-xylene solution of 1 milliliter of 0.05M adds in reaction system as the catalyzer of reaction, and after 30 minutes, reaction is warmed up to 230 ℃, keeps finishing in two hours, slowly cools to room temperature, filters and namely obtains target product.
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Effective date of registration: 20181120 Address after: 311800 No. 8 Xingye Road, Taozhu Street, Zhuji City, Shaoxing City, Zhejiang Province Patentee after: Zhuji Qingrong New Materials Co., Ltd. Address before: 312000 No. 50 Wangyun West Road, Taozhu Street, Zhuji City, Shaoxing City, Zhejiang Province Patentee before: Zhejiang ARTEX Fiber Co., Ltd. |