CN113463217B - Dimensionally stable layered elastomer - Google Patents
Dimensionally stable layered elastomer Download PDFInfo
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- CN113463217B CN113463217B CN202110781951.7A CN202110781951A CN113463217B CN 113463217 B CN113463217 B CN 113463217B CN 202110781951 A CN202110781951 A CN 202110781951A CN 113463217 B CN113463217 B CN 113463217B
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
- C08L67/025—Polyesters derived from dicarboxylic acids and dihydroxy compounds containing polyether sequences
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Abstract
The invention discloses a lamellar elastomer with stable size, which takes a thermoplastic polyester elastomer as a raw material to extrude a strip-shaped umbilical member, a lamellar object with a certain thickness is formed after curling and bonding, the umbilical member is in a hollow structure, the lamellar elastomer is repeatedly compressed for 8 ten thousand times with a compression force of 750N, the thickness loss rate is less than 6%, and the melting point-crystallization temperature (Tpm-Tpc) of the lamellar elastomer is 60-95 ℃. When the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer is 60 to 95 ℃, the crystallization speed becomes slow, the hollow rate of the umbilical member is improved, the bonding strength of the layered elastomer as a whole is improved, and the deformation retention rate is improved; the material has the best hot melting energy, and can further improve the joint strength of the layered elastomer continuous filament body; the amorphous region in the material is in a high-elastic state, and the molecular chain segment has strong movement capability, so that the polymer can obtain good toughness, and the improvement of the bonding strength and the toughness are both beneficial to improving the repeated compression-resistant dimensional stability of the layered elastomer product.
Description
Technical Field
The invention relates to a layered elastomer with a certain thickness, which is formed by coiling long fiber yarns, wherein the long fiber yarns are made of thermoplastic polyester elastomer, and the elastomer can be suitable for the fields of office chairs, sofas, beds and the like, in particular to a layered elastomer with stable size.
Background
The existing lamellar elastomer is usually manufactured by a spinning mode, specifically, a polyester elastomer in a molten state is extruded by a spinning plate at a certain speed and at a certain temperature, the extruded polyester elastomer falls into water to be cooled, continuous umbilical members are bent into rings, contact parts are welded with each other, two sides of the continuous umbilical members are flattened, and finally the continuous umbilical members are cut into a three-dimensional net structure with required size. Since existing layered elastomers are often used in related products such as cushions, mattresses, sofa cushions, etc., repeated compression durability (fatigue resistance) is required to be considered, and currently, more and more consumers are simultaneously focusing attention on repeated compression dimensional stability of the products.
Currently, as in CN105026632a, CN105026632a discloses that the fatigue resistance of a product is improved by enhancing the joint strength or by imparting a structural difference between the surface layer portion and the inner layer portion of the product, as in CN105683434B, CN105026632a discloses that the net-like structure has a repeated compressive residual strain of 15% or less at a constant displacement of 50% and CN105683434B discloses that the net-like structure has a repeated compressive residual strain (i.e., thickness loss rate) of 15% or less at a constant load of 750N. However, the layered elastomer product obtained by the prior method is actually tested, and as a result, the 750N repeated compression thickness loss rate of the product can only be maintained between 6 and 15%, and a lower repeated compression thickness loss rate, namely, the dimension is unstable, cannot be obtained. However, in practical product applications, especially in fields of mattresses and sofa cushions with high dimensional stability, the dimensional stability of the product is important after long-term use, and the layered elastomer product with the thickness loss rate of less than 15% cannot meet the requirements of customers.
Disclosure of Invention
The applicant has aimed at these drawbacks in the prior art and has found that by controlling the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer to be 60 to 95 ℃, a layered elastomer product having excellent dimensional stability, in which the layered elastomer product has a 750N constant load repeated compression of 8 ten thousand times and a thickness loss rate of less than 6%, is obtained, while the support factor and indentation hardness uniformity of the layered elastomer product are significantly improved.
The technical scheme adopted by the invention has the following beneficial effects:
a layered elastomer with stable size is prepared by extruding long filament body from thermoplastic polyester elastomer, curling and bonding to form a layered product with a certain thickness, wherein the filament body has a hollow structure, the layered elastomer is repeatedly compressed for 8 ten thousand times with a compression force of 750N to obtain a thickness loss rate of less than 6%, and the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer is 60-95deg.C. Generally, a product having a relatively high melting point and a relatively soft product having a low melting point can be obtained, but a polyester-based thermoplastic elastomer is a crystalline material, and all properties of the layered elastomer such as contact area of an umbilical member, bonding strength, the number of molecular chains in a high-elastic state in an amorphous region, and the like are closely related to the crystallization thereof. The lower the continuous filament extruded from the spinneret is, the more severely the continuous filament is stretched downward by gravity, that is, the lower the hollow ratio of the continuous filament is, and when the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer is 60 to 95 ℃, more preferably 65 to 85 ℃, the crystallization speed is lowered, the hollow ratio of the lowered continuous filament is improved, the higher the hollow ratio of the continuous filament of the layered elastomer means that the same heavy material can form more continuous filament, the higher the continuous filament density of the layered elastomer is in the same volume range, so that the contact surface area of the continuous filament can be increased, the number of bonding points is increased, the bonding strength of the layered elastomer as a whole is improved, and the deformation retention is improved. In addition, when the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer is 60 to 95 ℃, the material has the best hot-melting energy, and therefore, the bonding strength of the layered elastomer continuous filament can be further improved. When the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer is 60-95 ℃, the amorphous region in the material is in a high-elastic state, the molecular chain segment has strong movement capability, good toughness of the polymer is facilitated, and the improvement of the bonding strength and the toughness are both beneficial to the improvement of the repeated compression-resistant dimensional stability and the comfort of the layered elastomer product. The melting point-crystallization temperature (Tpm-Tpc) of the finally obtained layered elastomer product is 60-95 ℃ by controlling the material itself, the processing technology or the crystallization behavior of the layered elastomer, the thickness loss rate of the layered elastomer repeatedly compressed for 8 ten thousand times by 750N is less than 6%, and the layered elastomer is particularly suitable for manufacturing products with requirements on dimensional stability such as sofa cushions, mattresses and the like.
As a further improvement of the above technical scheme:
the shear viscosity of the raw material for producing the lamellar elastomer is 400-900 Pa.S at the test temperature of 230 ℃ and the shear speed of 10 (S-1). The viscosity of the polyester elastomer raw material under a certain shearing force is called shearing viscosity, the shearing viscosity also affects the crystallization performance of the lamellar elastomer and the hollow rate and the contact area of the linear body, when the shearing viscosity of the polyester elastomer raw material is 400-900 Pa.S at the test temperature of 230 ℃ and the shearing speed of 10 (S-1), more preferably 500-800 Pa.S, the linear body with higher hollow rate can be obtained, the contact area of the lamellar elastomer is larger, when the shearing viscosity is smaller than 400 Pa.S, the flowability of the material is high, the crystallization speed is high, the linear body with larger hollow rate cannot be obtained, the contact area of the linear body is small, the lamellar elastomer is unstable in size in the repeated compression fatigue resistance test, the uniformity of the collapse hardness of the whole product in the production process is poor, when the shearing viscosity is larger than 900 Pa.S, the material curing speed begins to be reduced, the material cannot form better hollow rate, the linear body is severely deformed and flattened, the loss rate of the lamellar elastomer in the repeated compression fatigue test is higher, and the uniformity of the collapse hardness of the whole product in the production process is poor.
The layered elastomer has a thickness loss rate of less than 4% by repeated compression of 8 ten thousand times with a compression force of 750N. The product with more excellent dimensional stability, wherein the thickness loss rate of 750N repeatedly compressed for 8 ten thousand times is smaller than 4%, is obtained by controlling the melting point-crystallization temperature (Tpm-Tpc) of the product to be 60-95 ℃, so that the consumer demand with higher requirement on the dimensional stability of the product is met.
The supporting factor of the layered elastomer is more than 3, more preferably more than 3.5, and the high supporting factor represents that the product has better comfort, the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer product is 60-95 ℃, the toughness of the layered elastomer product is better, and the product has better comfort.
The thermoplastic polyester elastomer raw material is obtained by blending polyether ester block copolymer elastomer with one or more of erucamide, ethylene bis-stearamide, oleamide, ethylene bis-oleamide, sodium 2,2' -methylene bis (4, 6-di-tert-butylphenyl) phosphate, carbodiimide, polycarbodiimide, isocyanate, talcum powder, stearate, long-chain linear saturated carboxylic acid sodium salt and SEBS elastomer with maleic anhydride functional groups. By adding different lubricants, transparencies, hydrolysis resistance agents, crosslinking agents, nucleating agents or other elastomers for modification, the shearing viscosity of raw materials is improved, the hardness and the melting point of the raw materials are reduced, and finally, a layered elastomer product with higher melting point-crystallization temperature (Tpm-Tpc) can be obtained, and products with good dimensional stability and high comfort can be obtained by modifying and adding auxiliary agents.
The soft segment of the thermoplastic polyester elastomer raw material is polytetrahydrofuran ether, and one or more of isophthalic acid, adipic acid, diol monomers or polycaprolactone are added in the polymerization process of the thermoplastic polyester elastomer raw material. The addition of one or more of the above monomers to the raw materials helps to increase the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer product, helps to increase the void fraction of the umbilical member, increases the bonding strength of the layered elastomer product, reduces the fatigue-resistant repeated compression thickness loss rate, and increases the product comfort.
The temperature of cooling water in the preparation process of the layered elastomer is lower than 60 ℃. When the temperature of cooling water is higher, heat cannot be quickly and completely dissipated after the umbilical member falls into a water bath, crystallization performance is affected, a product with a higher air heart rate cannot be obtained, latent heat of the lamellar elastomer cannot be released, the lamellar elastomer is easy to degrade and embrittle, and the bonding strength of the lamellar elastomer is reduced, so that the temperature of the cooling water is controlled to be lower than 60 ℃, and the obtained lamellar elastomer can be produced to have good toughness, dimensional stability and comfortableness.
The hollow rate of the lamellar elastomer umbilical body is 35-65%, the thickness of the lamellar elastomer is 20-200 mm, and the density is 30-100 kg/m 3 。
The standard deviation of the indentation hardness uniformity of the layered elastomer is 10-18N. When the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer product is 60-95 ℃, a layered elastomer product with excellent indentation hardness uniformity can be obtained, and the layered elastomer product is suitable for manufacturing mattress products with longer length, and the overall indentation hardness uniformity of the mattress products can be improved.
The layered elastomer has a bond strength of greater than 0.15MPa. When the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer product is 60 to 95 ℃ and the bonding strength is more than 0.15MPa, the product has a large number of bonding points and a large contact area of continuous umbilical members, so that the thickness loss rate is lower and the dimensional safety is more excellent after repeated compression for 8 ten thousand times with a compression force of 750N.
Detailed Description
Embodiments of the present invention are as follows.
The melting point-crystallization temperature (Tpm-Tpc) is related to the material itself of the layered elastomer and the process conditions for preparing the raw material, and the control of the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer can be considered from both aspects, for example, the properties of the material itself can be achieved by controlling the crystallization condition of the material during the preparation of the raw material, for example, other monomers in different ratios can be added in the polymerization step during the preparation, other acids in suitable ratios can be added in the polyester-based thermoplastic elastomer, for example, isophthalic acid, adipic acid, or glycol-based monomers or polycaprolactone and the like in suitable ratios, and glycol-based monomers such as ethylene glycol, propylene glycol, hexylene glycol and the like can be added, or a plurality of the above monomers can be added.
The properties of the material itself may also be controlled and modified by adding appropriate amounts of additives during blending, for example, different adjuvants may be added, lubricants, transparencies, hydrolysis inhibitors, cross-linking agents, nucleating agents or other elastomers with compatible functional groups (e.g. maleic anhydride, -MAH), lubricants such as erucamide, ethylene bis-stearamide, oleamide, ethylene bis-oleamide, transparencies such as sodium 2,2' -methylenebis (4, 6-di-tert-butylphenyl) phosphate, hydrolysis inhibitors such as carbodiimide, polycarbodiimide, cross-linking agents such as isocyanates, nucleating agents such as talc, stearates, long chain linear saturated carboxylic acid sodium salts, etc., other elastomers such as SEBS elastomers with maleic anhydride functionality may be added.
The molecular weight of the material can also influence the crystallization performance, the larger the molecular weight of the material is, the chain segments are difficult to pack, the larger the melting point-crystallization temperature (Tpm-Tpc) of the finally obtained layered elastomer is, and the smaller the molecular weight of the material is, the faster the molecular movement is, and the smaller the melting point-crystallization temperature (Tpm-Tpc) of the finally obtained layered elastomer is.
Raw material preparation process conditions such as extrusion temperature of materials, extrusion speed, high-temperature residence time of a screw, discharge environment cooling temperature and shaping cooling water temperature can influence the melting point-crystallization temperature (Tpm-Tpc) of a final lamellar elastomer product.
The polyester thermoplastic elastomer (A1, A2) is produced by polymerization, wherein dimethyl terephthalate (DMT), isophthalic acid and 1, 4-butanediol (1, 4-BD), polytetramethylene glycol (PTMEG), tetrabutyl titanate (TBT) catalyst and stabilizer Irganox1098 are used in the polymerization to carry out esterification reaction at 230 ℃, when the methanol stripping amount of a byproduct reaches more than 98% of theoretical value, the temperature is raised to 245 ℃ and the pressure is reduced to 100Pa to carry out polycondensation, and the polyether ester block copolymer elastomer is finally produced after polymerization to the required viscosity.
When the polyester-based thermoplastic elastomer (A3, B1, B2, C, D) is produced by polymerization, isophthalic acid is not used in the polymerization, and other raw materials and production conditions are the same as those of the polyester-based thermoplastic elastomer (A1, A2).
The modified polyester thermoplastic elastomer (B3) is obtained by blending and granulating 92wt% of the polyester thermoplastic elastomer B2 and 8% of the styrene thermoplastic elastomer at 235 ℃ by using a double screw, wherein the styrene thermoplastic elastomer can be SEBS elastomer with the hardness of 71A and containing 1.7% of maleic anhydride grafting rate, and commercial products such as FG 1901G polymer products of Koteng U.S.A.
The polyester elastomer raw material formulation obtained is shown in table 1, and the polyester elastomer raw material characteristic hardness, melting point, and shear viscosity are shown in table 2, wherein the shear viscosity is controlled by controlling the production condition parameters such as polymerization time.
Table 1:
table 2:
the specific test method is as follows:
1. thickness: the layered elastomer was cut into 3cm×3cm samples, 3 samples were randomly selected, the thickness of the product was measured using a thickness gauge, and the average value was calculated.
2. Density: the layered elastomer was placed in an oven set at 80 c for 3hr to ensure moisture removal, the length, width and height of the product were measured to calculate the volume, and the density was calculated by weighing with a three-position precision balance after the decimal point was reached, and dividing the weight by the volume.
3. Wire diameter: 5 fibers were randomly drawn from the layered elastomer, the diameter at 3 was measured using a 20-fold optical microscope with a scale, the average diameter of each fiber was calculated, and the average value of 5 fibers was calculated.
4. Hollow ratio: 1 piece of lamellar elastomer sample with the size of 3cm x 3cm is randomly selected, 6 pieces of samples are randomly selected within the range of plus or minus 30% of the area of the center point in the thickness direction of the sample, fiber section photos are obtained by using an optical microscope, the area a of the hollow part and the total area b of the fiber containing the hollow part are calculated according to the section photos, the hollow ratio=a/b x 100%, and the average value is calculated.
5. Melting point and crystallization temperature difference (Tpm-Tpc): 3 lamellar elastomer samples with the size of 3cm multiplied by 3cm are randomly selected, and tested by using an ISO11357-3 plastic Differential Scanning Calorimetry (DSC) method, the heating rate is 20 ℃/min until the melting area is extrapolated to 30 ℃, the highest peak of the melting area is the melting point Tpm, and the first thermal cycle data is taken to obtain the melting point value. And then cooling at a cooling speed of 20 ℃/min until the temperature is 50 ℃ lower than the expected crystallization area, wherein the peak of the crystallization area is the crystallization temperature Tcm, the difference between the melting point and the crystallization temperature is Tpm-Tpc, and calculating the average value of 3 samples.
6. 40% indentation hardness test: and (3) placing a layered elastomer sample between an upper pressure plate and a lower pressure plate at a constant temperature of 23 ℃, compressing to 40% under the test speed of 100mm/min, compressing the product downwards by the upper pressure plate, sensing the pressure by a load cell at the upper end, converting the pressure into a voltage signal, transmitting the voltage signal to a display for analysis, displaying the pressure value on a screen, and performing test three times to obtain an average value.
7. Standard deviation of indentation hardness uniformity: 3 samples are respectively taken at the left, middle and right (20%, 50% and 80% positions) of the discharging position in the width direction perpendicular to the discharging direction in the production process of the layered elastomer, the sample size is 40cm x 40cm, the 3 samples are positioned on the same plane of the layered elastomer, one sample is taken every 3 minutes, 30 samples are taken within 30 minutes, 40% indentation hardness test is carried out on each sample, and then the standard deviation of the 30 samples is calculated.
8. Support factor test: and (3) placing the layered elastomer between an upper pressure plate and a lower pressure plate at a constant temperature of 23 ℃, respectively compressing to 25% and 65% of strain at a test speed of 100mm/min, compressing the product downwards by the upper pressure plate, sensing the pressure by a pressure sensor at the upper end, converting the pressure into a voltage signal, transmitting the voltage signal to a display for analysis, displaying the pressure value on a screen, and performing test three times to obtain an average value. The 65% pressure value is divided by the 25% pressure value by the support factor.
9. Fatigue-resistant repeated compression thickness loss rate: the layered elastomer was placed on the lower platform of a repeated compression tester at a constant temperature of 23℃according to the ISO3385 test standard, the product was repeatedly compressed at a compression force of 750N at a frequency of 70 times per minute, and the performance of the product was evaluated after 8 ten thousand times of compression. Fatigue resistance repeated compression thickness loss rate = (thickness before product test-thickness after product test)/thickness before product test, 3 samples were measured and averaged.
10. Joint strength: cutting the layered elastomer to obtain 3 parts of samples with the size of 17 cm/3 cm, wherein the thickness is the original layered elastomer thickness, stretching the layered elastomer by a universal tensile machine to obtain a maximum force value KN according to the measurement method of ISO527, and measuring 3 samples to obtain an average value.
11. Shear viscosity: the polyester elastomer raw material was tested by using a capillary rheometer with reference to the test standard of ISO11443 at a temperature of 220 ℃ and a shear rate of 10 (s-1), to obtain a shear viscosity number.
Example 1
Feeding a raw material of a polyester elastomer A1 into an extruder, heating to a molten state at 230 ℃ in the extruder, conveying to a spinning plate through a metering pump, spraying continuous umbilical member fibers from the spinning plate, dropping into water, bending into a ring, welding contact parts among the umbilical members, keeping the traction rate at 0.6g/min, adopting infrared heat preservation between the spinning plate and a lower water tank, compressing the woven continuous umbilical member fibers in warm water at 25 ℃ through a die to be flattened on two sides, and finally forming to obtain a three-dimensional lamellar elastomer, testing the lamellar elastomer through the method, wherein physical parameters are shown in table 2, and the net structure density of the obtained lamellar elastomer is 55kg/m 3 The melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer is 82 ℃, the 40% indentation hardness is 232N, the hollow rate is 47%, the bonding strength is 0.17MPa, the thickness loss rate after fatigue resistance repeated compression is 3.3%, the dimensional stability of the layered elastomer is good, and the indentation hardness uniformity and comfort are good.
Example 2
Concrete embodimentsThe procedure is as in example 1, but the starting materials used are changed to polyester elastomer B1, the resulting layered elastomer having a network density of 60kg/m 3 The melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer is 69 ℃, the 40% indentation hardness is 214N, the hollow rate is 39%, the bonding strength is 0.16MPa, the thickness loss rate after fatigue resistance and repeated compression is 3.9%, and the layered elastomer has good dimensional stability, indentation hardness uniformity and comfort.
Example 3
The process was carried out in the same manner as in example 1, except that the starting material used was changed to polyester elastomer B3, and the resulting layered elastomer had a network density of 60kg/m 3 The melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer is 71 ℃, the 40% indentation hardness is 181N, the hollow rate is 44%, the bonding strength is 0.18MPa, the thickness loss rate after fatigue resistance and repeated compression is 3.1%, and the layered elastomer has good dimensional stability, indentation hardness uniformity and comfort.
Example 4
The procedure is as in example 1, but the starting materials used are changed to polyester elastomer D, the resulting layered elastomer having a network density of 70kg/m 3 The melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer is 81 ℃, the 40% indentation hardness is 201N, the hollow rate is 51%, the bonding strength is 0.17MPa, the thickness loss rate after fatigue resistance and repeated compression is 2.7%, and the layered elastomer has good dimensional stability, indentation hardness uniformity and comfort.
Comparative example 1
The process was carried out in the same manner as in example 1, except that the starting material used was changed to polyester elastomer A2, and the resulting layered elastomer had a network density of 55kg/m 3 The melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer was 96 ℃, the 40% indentation hardness was 225N, the indentation hardness uniformity standard deviation was as high as 38N, the void fraction was 34%, the bonding strength was 0.13MPa, the thickness loss rate after repeated fatigue compression resistance was 7.3%, the dimensional stability of the layered elastomer was quite poor, and the indentation hardness uniformity was very poor.
Comparative example 2
The process is the same as in example 1, but the starting materials used are changed to polyester elastomersA3, the network density of the resulting layered elastomer was 55kg/m 3 The melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer was 49 ℃,40% indentation hardness was 261N, indentation hardness uniformity standard deviation was 21N, hollow rate was 26%, joining strength was 0.07MPa, thickness loss rate after fatigue resistance repeated compression was 8.8%, dimensional stability of the layered elastomer was quite poor, and comfort was poor.
Comparative example 3
The process was carried out as in example 1, except that the starting material used was changed to polyester elastomer B1, the setting temperature of the cooling water was changed to 80℃and the network density of the resulting layered elastomer was 60kg/m 3 The melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer was 54 ℃, the 40% indentation hardness was 225N, the indentation hardness uniformity standard deviation was 26N, the hollow rate was 29%, the joining strength was 0.08MPa, the thickness loss rate after repeated fatigue compression resistance was 6.7%, the dimensional stability of the layered elastomer was quite poor, and the indentation hardness uniformity and comfort were poor.
Comparative example 4
The procedure is as in example 1, but the starting material used is changed to polyester elastomer B2, the network density of the lamellar elastomer being 60kg/m 3 The melting point-crystallization temperature (Tpm-Tpc) of the obtained layered elastomer was 53 ℃,40% indentation hardness was 231N, indentation hardness uniformity standard deviation was 22N, hollow rate was 31%, joining strength was 0.08MPa, thickness loss rate after fatigue resistance repeated compression was 6.4%, dimensional stability of the layered elastomer was quite poor, indentation hardness uniformity and comfort were poor.
Comparative example 5
The procedure is as in example 1, but the starting material used is changed to polyester elastomer C, the network density of the lamellar elastomer being 70kg/m 3 The melting point-crystallization temperature (Tpm-Tpc) of the obtained layered elastomer was 59 ℃,40% indentation hardness was 227N, indentation hardness uniformity standard deviation was 25N, hollow rate was 34%, joining strength was 0.09MPa, thickness loss rate after fatigue resistance repeated compression was 6.1%, dimensional stability of the layered elastomer was quite poor, indentation hardness uniformity and comfort were poor.
The layered elastomer products of examples 1 to 4 and comparative examples 1 to 5 were tested by the above-described test methods, and the test results obtained are shown in Table 3.
Table 3:
in comparative example 1 and comparative example 1, isophthalic acid was added to the raw materials, but the fatigue-resistant repeated compression thickness loss rate of example 1 was only 3.3%, whereas the fatigue-resistant repeated compression thickness loss rate of comparative example 1 was 7.3%, considering that the polyester elastomer raw material A2 used in comparative example 1 had a shear viscosity of 998 Pa ·s, and when the shear viscosity was too high, the curing rate of the polyester elastomer material was lowered, heat was not rapidly and completely dissipated after the umbilical members were dropped into the water bath, curing was not complete, but the material was not formed into a good hollow rate, and the hollow rate was low, only 35%; the linear body is severely deformed and flattened, so that the layered elastomer is unstable in size after fatigue test, low in joint strength and high in fatigue-resistant repeated compression thickness loss rate up to 7.3%; and the uniformity in the production process is poor, and the standard deviation of the indentation hardness uniformity is as high as 38N; and results in a final layered elastomer product with a higher melting point-crystallization temperature (Tpm-Tpc) and an inability of latent heat of the layered elastomer to release, resulting in a layered elastomer that is easily degraded and brittle, and a decrease in the bond strength between layered elastomer strands of only 0.13 MPa; the layered elastomer has poor toughness and poor comfort, and the support factor is only 2.9. Under the condition that the contents of polytetrahydrofuran ether and isophthalic acid in the raw materials are the same, the difference of the shearing viscosity can also cause the difference of the final finished products, the addition of isophthalic acid is not necessarily capable of obtaining the products with low fatigue resistance repeated compression thickness loss rate and stable size, and the control of the shearing viscosity is also one of key factors. When the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer is more than 95 ℃, the layered elastomer is poor in compression dimensional stability, uniformity and comfort.
Comparative example 1 and comparative example 2, both of which were identical in spinning temperature, cooling water temperature, and filament output control during production, were different in that example 1 added isophthalic acid to the raw material, comparative example 2 did not add isophthalic acid to the raw material, and the final produced layered elastomer product was low in melting point-crystallization temperature (Tpm-Tpc) of only 49 ℃, and solidification was fast after the continuous filament body was discharged from the spinneret considering that it might be small, and most filament bodies had completed solidification before the filament body was dropped into the water bath, resulting in poor hot-melt ability of the layered elastomer. Since most of the umbilical members completed curing earlier, the hollow rate of the umbilical members was low, only 26%, the continuous umbilical member density of the layered elastomer was low in the same volume range, and the number of bonding points was small, and therefore the bonding strength of the layered elastomer produced was reduced, only 0.07MPa; in addition, the crystallization particles are larger, the amorphous area is greatly reduced, the molecular chain in a high-elastic state is reduced, the movement capability of the molecular chain segment is weaker, the toughness of the layered elastomer is poorer, the dimensional stability and the comfort are seriously affected, the fatigue-resistant repeated compression thickness loss rate is as high as 8.8%, the support factor is only 2.6, and the uniformity in the production process is poor. It can be seen that the addition of isophthalic acid can help to increase the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer product, help to increase the void fraction of the umbilical member, enhance the bonding strength of the layered elastomer product, and reduce the fatigue-resistant repeated compression thickness loss rate. The shear viscosity of comparative example 2 was Pa.S, and it was found that the shear viscosity was not the only influencing factor affecting the dimensional stability and comfort of the final product, and even if the raw material preparation with the shear viscosity of 400 to 900 Pa.S was selected, the product with excellent dimensional stability and comfort could not necessarily be obtained, but the parameter of melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer product could correctly evaluate whether the product had excellent dimensional stability and comfort.
Comparative example 2 and comparative example 3 differ only in that the temperature of the shaping cooling water of example 2 is 20 ℃, the temperature of the shaping cooling water of comparative example 3 is 80 ℃, the melting point-crystallization temperature (Tpm-Tpc) of the finally prepared lamellar elastomer product is low, the hollow rate is low, only 29%, it is suspected that the heat cannot be rapidly and completely dissipated after the umbilical member falls into the water bath, the crystallization performance is affected, the product with a higher hollow rate cannot be obtained, the latent heat of the lamellar elastomer cannot be released, the lamellar elastomer is easily degraded and easily embrittled, the bonding strength of the lamellar elastomer is reduced, the toughness of the lamellar elastomer is poor, the dimensional stability and the comfort are poor, the fatigue-resistant repeated compression thickness loss rate is as high as 6.7%, the support factor is only 2.8, and the uniformity in the production process is poor. It can be seen that the cooling water temperature during the production process also affects the dimensional stability and comfort of the final layered elastomer product, and that products with good dimensional stability and high comfort cannot be obtained when the water temperature is too high.
In comparative examples 2 and 4, the polyester elastomer raw material A2 used in comparative example 4 has a molecular weight of 2000, the starting material has a shear viscosity of Pa.S, and a lower shear viscosity results in a finally produced layered elastomer product having a lower melting point-crystallization temperature (Tpm-Tpc) of only 53 ℃, which is the same as in comparative example 2, and the layered elastomer product has a low hollow ratio, a low density of continuous filament bodies of the layered elastomer in the same volume range, and a small number of bonding points, and therefore, the produced layered elastomer has a low bonding strength, a poor toughness of the layered elastomer, a poor dimensional stability and comfort, and a poor uniformity in the production process. Therefore, if isophthalic acid is not added into the raw materials, the polyester elastomer raw materials with higher shearing viscosity can be selected, and the lamellar elastomer product with good dimensional stability and high comfort level can be prepared, and the influence of the molecular weight of polytetrahydrofuran ether, namely the material weight, on the stability and the comfort level of the product is smaller than that of the shearing viscosity.
In comparative examples 3 and 4, the polyester elastomer raw material B3 used in example 3 was obtained by blending the polyester-based thermoplastic elastomer B2 and 8% of the styrene-based thermoplastic elastomer in comparative example 4, and the modified polyester elastomer raw material B3 increased the shear viscosity of the polyester-based thermoplastic elastomer B2, decreased the hardness and melting point of the raw material, increased the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer product, and after the melting point-crystallization temperature (Tpm-Tpc) was increased, the crystallization speed was slowed down, the hollow ratio of the descending continuous filament was increased, the hollow ratio of the continuous filament of the layered elastomer was larger, meaning that the same heavy material could form more continuous filament, the continuous filament density of the layered elastomer was higher in the same volume range, so that the contact surface area of the continuous filament could be increased, the number of bonding points was increased, and the bonding strength of the layered elastomer as a whole was increased; in addition, the crystallization particles are smaller, the molecular chain in a high-elasticity state is increased, the movement capacity of the molecular chain segment is higher, the toughness of the layered elastomer is better, the hollowness can reach 44%, the fatigue-resistant repeated compression thickness loss rate is only 4.1%, the support factor can reach 4.1, and the uniformity in the production process is good. It can be seen that products with good dimensional stability and high comfort can be obtained by modifying and adding auxiliary agents.
In comparative examples 4 and 5, the polyester elastomer raw material used in comparative example 5 had a shear viscosity of 387 Pa.S, and the shear viscosity was too low, resulting in a finally produced layered elastomer product having a melting point-crystallization temperature (Tpm-Tpc) of only 59℃and, when the shear viscosity was less than 400 Pa.S, the material fluidity was fast, the crystallization speed was fast, and the linear body could not obtain a large hollow rate and a large contact area, so that the layered elastomer was unstable in size after fatigue test, and had poor uniformity in production. The difference between example 4 and comparative example 5 is only that the difference in the polytetrahydrofuran ether content and the shear viscosity in the raw materials and the spinning temperature of example 4 are low, the polytetrahydrofuran ether content of example 4 is 68%, the molecular weight of polytetrahydrofuran ether is 2000, the molecular weight of the material itself is large, the chain segments are hard to pile up, the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer product of example 4 becomes large, and the melting point-crystallization temperature (Tpm-Tpc) of the layered elastomer product of example 4 can reach 81 ℃, so that a product with higher hollow rate and better dimensional stability can be obtained, and it can be seen that the molecular weight of the material itself has a certain influence on the dimensional stability and comfort of the product. However, the most important factor is still the shear viscosity, and when the shear viscosity is 635 Pa S of example 4, a layered elastomer product with excellent dimensional stability and high comfort can be obtained even at a low spinning temperature (220 ℃ in example 4).
The above description is illustrative of the invention and is not intended to be limiting, and the invention may be modified in any form without departing from the spirit of the invention.
Claims (8)
1. A dimensionally stable layered elastomer, which is produced by extruding a thermoplastic polyester elastomer as a raw material into a long-strip-shaped filament body, and forming a layered product of a certain thickness after crimping and bonding, wherein the filament body has a hollow structure, characterized in that: the thickness loss rate of the lamellar elastomer after repeated compression for 8 ten thousand times with a compression force of 750N is less than 6%, and the melting point-crystallization temperature (Tpm-Tpc) of the lamellar elastomer is 60-95 ℃; the thermoplastic polyester elastomer raw material is obtained by blending polyether ester block copolymer elastomer with one or more of erucic acid amide, ethylene bis-stearic acid amide, oleic acid amide, ethylene bis-oleic acid amide, sodium 2,2' -methylene bis (4, 6-di-tert-butylphenyl) phosphate, carbodiimide, polycarbodiimide, isocyanate, talcum powder oleic acid amide, ethylene bis-oleic acid amide, long-chain linear saturated carboxylic acid sodium salt and SEBS elastomer with maleic anhydride functional groups; the soft segment of the thermoplastic polyester elastomer raw material is polytetrahydrofuran ether, and one or more of isophthalic acid, adipic acid, diol monomers or polycaprolactone are added in the polymerization process of the thermoplastic polyester elastomer raw material.
2. Dimensionally stable layered elastomer according to claim 1, wherein: the shearing viscosity of the raw materials for producing the layered elastomer is 400-900 Pa.S.
3. Dimensionally stable layered elastomer according to claim 1, wherein: the layered elastomer has a thickness loss rate of less than 4% by repeated compression of 8 ten thousand times with a compression force of 750N.
4. Dimensionally stable layered elastomer according to claim 1, wherein: the layered elastomer has a support factor greater than 3.
5. Dimensionally stable layered elastomer according to claim 1, wherein: the hollow rate of the layered elastomer filament is 35-65%.
6. Dimensionally stable layered elastomer according to claim 1, wherein: the temperature of cooling water in the preparation process of the layered elastomer is lower than 60 ℃.
7. Dimensionally stable layered elastomer according to claim 1, wherein: the thickness of the layered elastomer is 20 mm-200 mm.
8. Dimensionally stable layered elastomer according to claim 1, wherein: the density of the lamellar elastomer is 30-100 kg/m 3 。
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