CN115716902A - Organic silicon modified wear-resistant TPU (thermoplastic polyurethane), and preparation method and application thereof - Google Patents
Organic silicon modified wear-resistant TPU (thermoplastic polyurethane), and preparation method and application thereof Download PDFInfo
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- CN115716902A CN115716902A CN202211472100.5A CN202211472100A CN115716902A CN 115716902 A CN115716902 A CN 115716902A CN 202211472100 A CN202211472100 A CN 202211472100A CN 115716902 A CN115716902 A CN 115716902A
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Abstract
The invention belongs to the technical field of thermoplastic polyurethane elastomers, and particularly relates to an organic silicon modified high-wear-resistance TPU, and a preparation method and application thereof. The composite material mainly comprises the following substances in percentage by mass: 45-65% polymer polyol; 25-40% of diisocyanate; 6.5 to 15 percent of chain extender; 5-15% of an organosilicon modifier; 2-10% of an initiator. The preparation method comprises the following steps: producing reactive hydroxyl organic silicon modified TPU particles by using a double-screw extruder; and mixing the prepared reactive hydroxyl organic silicon modified TPU particles with an initiator in a molten state to perform a crosslinking reaction to obtain the organic silicon modified TPU. After being filmed by siloxane ester under the action of an initiator, the siloxane ester is gathered on the surface of the TPU, thereby obviously improving the wear resistance, water repellency and antifouling property of the TPU product. The organic silicon modified high-wear-resistance TPU prepared by the invention is mainly applied to shoe material products and can also be applied to industrial applications such as trundles, sealing elements and the like.
Description
Technical Field
The invention belongs to the technical field of thermoplastic polyurethane elastomers, and particularly relates to an organic silicon modified wear-resistant TPU, and a preparation method and application thereof.
Background
Thermoplastic polyurethane elastomer (TPU) has excellent tensile strength, tensile resistance and aging resistance, and is a mature environment-friendly chemical material. It has the characteristics of high strength, good toughness, aging resistance, weather resistance and the like which cannot be compared with other plastic materials; meanwhile, the fabric has a plurality of excellent functions such as high waterproofness and moisture permeability, wind resistance, cold resistance, antibiosis, mildew resistance, heat preservation, ultraviolet resistance and the like. At present, TPU is widely applied to plastic products such as shoe materials, clothes, toys and the like.
However, since TPU has a linear molecular structure, it is not perfect in wear resistance, solvent resistance, high temperature resistance, etc., which are required in many fields of use, such as industrial safety shoes for mines, casters, seals, etc., and it is required that TPU has good wear resistance.
Patent CN113861668A discloses a high refractive index, high wear resistant TPU particle and a preparation method thereof, but the method for preparing wear resistant TPU is complex and not environment-friendly, and has a certain loss to the performance of TPU itself. Patent CN108034038A discloses a high wear-resistant TPU for cable housings and a preparation method thereof, but the preparation method is complicated and cannot be continuously produced in large quantities. Patent CN113637139A discloses an organosilicon modified TPU composition and a preparation method thereof, but the above patent has a problem that the organosilicon modifier is added after melting TPU particles, which is equivalent to secondary processing, and particularly, the performance loss of TPU is large in a mass production process.
Therefore, it is an important subject to develop a highly abrasion resistant TPU material having high abrasion resistance without loss of processability and mechanical properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an organosilicon modified wear-resistant TPU; the invention also provides a preparation method of the composition, which is scientific, reasonable, simple and feasible; the invention also provides the application thereof.
The organic silicon modified wear-resistant TPU disclosed by the invention comprises the following substances in percentage by mass:
wherein:
the sum of the mass fractions of the polymer polyol, the diisocyanate and the chain extender is 100 percent, and the mass fractions of the organic silicon modifier and the initiator are the proportion on the basis;
the initiator is a cationic photoinitiator, and the cationic luminous initiator is triarylsiloxane.
The number average molecular weight of the polymer polyol is 1000-2000, and the polymer polyol is one or more of polyethylene glycol adipate glycol, polybutylene adipate glycol, polyhexamethylene glycol adipate glycol, polyethylene glycol adipate-butanediol glycol, polybutylene glycol adipate-hexanediol glycol, polybutylene sebacate glycol, polyhexamethylene glycol sebacate glycol or polyethylene glycol sebacate glycol.
The diisocyanate is one of diphenylmethane diisocyanate, p-phenyl diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 1, 4-cyclohexyl diisocyanate or decane-1, 10-diisocyanate.
The chain extender is a compound of a chain extender 1 and a chain extender 2, wherein the chain extender 1 is one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol and methyl propylene glycol.
The chain extender 2 is trimethylolpropane, and the chain extender 1: the mass ratio of the chain extender 2 is 9:1.
the organic silicon modifier is a reactive hydroxyl organic silicon modifier, preferably dihydroxy polydimethylsiloxane.
The preparation method of the organic silicon modified wear-resistant TPU comprises the following steps:
step 1: adding polymer polyol, diisocyanate and a chain extender into a dynamic mixer through a pouring metering system according to the formula mass ratio, mixing, adding the mixed material into a zone 1 of a twin-screw granulation system with 14 temperature zones, keeping the temperature of twin screws at 140-220 ℃, adding a quantitative organic silicon modifier into a zone 10 of the twin-screw granulation system to enable the R value of TPU to reach 1.01, and carrying out underwater granulation to obtain reactive hydroxyl organic silicon modified TPU particles;
step 2: and (3) mixing the reactive hydroxyl organic silicon modified TPU particles obtained in the step (1) with an initiator in a mixer to perform a crosslinking reaction to prepare the organic silicon modified wear-resistant TPU.
Wherein:
the rotating speed of the screw rod in the step 1 is 180-220rmp.
The temperature of the screw in the step 1 is set as follows:
region 1-3: 160-180 ℃;
zone 4-10: 180-220 ℃;
regions 11 to 14: 140-160 ℃;
underwater pelletizing temperature: 160-180 ℃.
The organic silicon modified wear-resistant TPU prepared by the invention is mainly applied to shoe material products and can also be applied to industrial applications such as trundles, sealing elements and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the organic silicon modified wear-resistant TPU disclosed by the invention, the reactive hydroxyl organic silicon modifier is used for modifying the TPU, and organic silicon and crosslinkable groups are introduced into a molecular chain of the TPU, so that the organic silicon and crosslinkable groups are gradually transferred to the surface of the TPU to form an organic silicon layer due to poor compatibility with a TPU chain segment. The TPU of the type is heated to a molten state, and in a high-temperature environment, the initiator initiates a crosslinking group to perform a crosslinking reaction, so that the processing easiness, the wear resistance and the fatigue resistance test capability of the TPU are improved on the premise of not losing the processing and mechanical properties of the normal TPU; and the problems of short service life and quick abrasion of the existing TPU product under a specific working condition are solved.
(2) The invention adopts a mode of compounding two chain extenders to improve the mechanical strength and the processing performance of the TPU; the initiator used in the invention is a cationic photoinitiator, which is different from the conventional initiator, and the photoinitiator can be added in post processing and can generate an initiating effect without heating TPU, thereby reducing the production cost; the reactive organosilicon is introduced in the production process of the TPU particles, and is different from the conventional modification embodiment in that the TPU particles are added after being melted, so that the loss of the performance of the TPU due to secondary processing is avoided, and the original performance of the TPU is reserved. The preparation method is simple, feasible, scientific and reasonable, has low cost and high efficiency, and does no harm to operators and the surrounding environment.
(3) The wear-resistant TPU modified by organic silicon prepared by the invention improves the wear resistance and the aging resistance, solves the problems of short service life and quick wear of the existing TPU product in a special operation environment, and can be widely applied to the product fields of soles, trundles, sealing elements and the like.
Detailed Description
All starting materials used in the examples are commercially available, except where specifically indicated.
Example 1
An organic silicon modified wear-resistant TPU comprises the following raw materials in percentage by mass:
the preparation process comprises the following steps:
step 1: adding polybutylene adipate glycol (Mn = 2000), diphenylmethane diisocyanate, 1, 4-butanediol and trimethylolpropane into a dynamic mixer according to the formula mass ratio through a pouring metering system for rapid mixing, adding the mixed material into a 1 st zone of a twin-screw granulation system with 14 temperature zones, adding quantitative dihydroxy polydimethylsiloxane into a 10 th zone of the twin-screw granulation system to enable the R value of TPU to reach 1.01, and carrying out underwater granulation to obtain reactive hydroxyl organosilicon modified TPU particles;
and 2, step: and (3) mixing the reactive hydroxyl organic silicon modified TPU particles obtained in the step (1) with triaryl siloxane in a mixer to perform a crosslinking reaction to prepare the organic silicon modified wear-resistant TPU.
The rotating speed of the screw rod in the step 1 is 200rmp.
The temperature of the screw in the step 1 is set as follows:
region 1-3: 170 ℃;
zone 4-10: 200 ℃;
11-14 region: 150 ℃;
underwater pelletizing temperature: 170 deg.C.
Example 2
An organic silicon modified wear-resistant TPU comprises the following raw materials in percentage by mass:
the preparation process comprises the following steps:
step 1: adding polyethylene glycol adipate glycol (Mn = 2000), isophorone diisocyanate, ethylene glycol and trimethylolpropane into a dynamic mixer through a pouring metering system according to the formula mass ratio for rapid mixing, adding the mixed material into a zone 1 of a double-screw granulation system with 14 temperature zones, adding quantitative dihydroxy polydimethylsiloxane into a zone 10 of the double-screw granulation system to enable the R value of TPU to reach 1.01, and carrying out underwater granulation to obtain reactive hydroxy organosilicon modified TPU particles;
and 2, step: and (2) mixing the reactive hydroxyl organic silicon modified TPU particles obtained in the step (1) with triaryl siloxane ether in a mixer to perform a crosslinking reaction to prepare the organic silicon modified wear-resistant TPU.
The rotating speed of the screw rod in the step 1 is 180rmp.
The temperature of the screw in the step 1 is set as follows:
region 1-3: 160 ℃;
zone 4-10: 180 ℃;
11-14 region: 140 ℃;
underwater pelletizing temperature: at a temperature of 160 ℃.
Example 3
An organic silicon modified wear-resistant TPU comprises the following raw materials in percentage by mass:
the preparation process comprises the following steps:
step 1: adding polybutylene adipate diol (Mn = 2000), toluene diisocyanate, methyl propylene glycol and trimethylolpropane into a dynamic mixer through a pouring metering system according to the formula mass ratio for rapid mixing, adding the mixed material into a zone 1 of a double-screw granulation system with 14 temperature zones, adding a certain amount of dihydroxy polydimethylsiloxane into a zone 10 of the double-screw granulation system to enable the R value of TPU to reach 1.01, and carrying out underwater granulation to obtain reactive hydroxy organosilicon modified TPU particles;
step 2: and (3) mixing the reactive hydroxyl organic silicon modified TPU particles obtained in the step (1) with triaryl siloxane in a mixer to perform a crosslinking reaction to prepare the organic silicon modified wear-resistant TPU.
The rotating speed of the screw in the step 1 is 220rmp.
The temperature of the screw in the step 1 is set as follows:
region 1-3: 180 ℃;
zone 4-10: 220 ℃;
regions 11 to 14: 160 ℃;
underwater pelletizing temperature: 180 ℃ is carried out.
Example 4
An organic silicon modified wear-resistant TPU comprises the following raw materials in percentage by mass:
the preparation process comprises the following steps:
step 1: adding polyethylene glycol adipate glycol (Mn = 2000), diphenylmethane diisocyanate, 1, 6-hexanediol and trimethylolpropane into a dynamic mixer through a pouring metering system according to the formula mass ratio for rapid mixing, adding the mixed material into a zone 1 of a twin-screw granulation system with 14 temperature zones, adding quantitative dihydroxy polydimethylsiloxane into a zone 10 of the twin-screw granulation system to enable the R value of TPU to reach 1.01, and carrying out underwater granulation to obtain reaction type hydroxy organosilicon modified TPU particles;
step 2: and (3) mixing the reactive hydroxyl organic silicon modified TPU particles obtained in the step (1) with triaryl siloxane in a mixer to perform a crosslinking reaction to prepare the organic silicon modified wear-resistant TPU.
The rotating speed of the screw rod in the step 1 is 200rmp.
The temperature of the screw in the step 1 is set as follows:
region 1-3: 170 ℃;
zone 4-10: 200 ℃;
11-14 region: 150 ℃;
underwater pelletizing temperature: 170 deg.C.
Comparative example 1
The raw materials and the mass fraction thereof are as follows:
polybutylene adipate diol (Mn = 2000) 58,
32.8 parts of diphenylmethane diisocyanate,
9.2 of 1, 4-butanediol;
the preparation process comprises the following steps:
adding polybutylene adipate diol (Mn = 2000), diphenylmethane diisocyanate and 1, 4-butanediol into a dynamic mixer through a pouring metering system according to the formula mass ratio for rapid mixing, adding the mixed material into a zone 1 of a double-screw granulation system with 14 temperature zones to enable the R value of TPU to reach 1.01, and carrying out underwater granulation to obtain TPU particles;
the rotating speed of the screw is 200rmp.
The temperature of the screw is set as follows:
region 1-3: 170 ℃;
zone 4-10: 200 ℃;
11-14 region: 150 ℃;
underwater pelletizing temperature: 170 deg.C.
Comparative example 2
The raw materials and the mass fraction thereof are as follows:
the preparation process is the same as that of comparative example 1.
Comparative example 3
The raw materials and the mass fraction thereof are as follows:
the preparation process comprises the following steps:
step 1: adding polybutylene adipate glycol (Mn = 2000), diphenylmethane diisocyanate, 1, 4-butanediol and trimethylolpropane into a dynamic mixer through a pouring metering system according to the formula mass ratio for rapid mixing, adding the mixed materials into a zone 1 of a twin-screw granulation system with 14 temperature zones, and carrying out underwater granulation to obtain TPU particles;
step 2: heating the TPU particles prepared in the step 1 to a molten state, and then mixing the heated TPU particles with dihydroxyl polydimethylsiloxane to enable the R value of the TPU to reach 1.01;
and 3, step 3: and (3) mixing the reactive hydroxyl organic silicon modified TPU obtained in the step (2) with triaryl siloxane in a mixing machine to perform a crosslinking reaction to prepare the organic silicon modified crosslinked TPU.
The rotating speed of the screw rod in the step 1 is 200rmp.
The temperature of the screw in the step 1 is set as follows:
region 1-3: 170 ℃;
zone 4-10: 200 ℃;
regions 11 to 14: 150 ℃;
underwater pelletizing temperature: 170 deg.C.
Comparative example 4
The raw materials and the mass fraction thereof are as follows:
the preparation process comprises the following steps:
step 1: adding polybutylene adipate glycol (Mn = 2000), diphenylmethane diisocyanate, 1, 4-butanediol and trimethylolpropane into a dynamic mixer according to the formula mass ratio through a pouring metering system for rapid mixing, adding the mixed material into a 1 st zone of a twin-screw granulation system with 14 temperature zones, adding quantitative dihydroxy polydimethylsiloxane into a 10 th zone of the twin-screw granulation system to enable the R value of TPU to reach 1.01, and carrying out underwater granulation to obtain reactive hydroxyl organosilicon modified TPU particles;
step 2: and (3) heating the reactive hydroxyl organic silicon modified TPU particles obtained in the step (1) to a molten state, and mixing the heated reactive hydroxyl organic silicon modified TPU particles with benzoyl peroxide tert-butyl ester to perform a crosslinking reaction to obtain the organic silicon modified crosslinked TPU.
The rotating speed of the screw rod in the step 1 is 200rmp.
The temperature of the screw in the step 1 is set as follows:
region 1-3: 170 ℃;
zone 4-10: 200 ℃;
regions 11 to 14: 150 ℃;
underwater pelletizing temperature: 170 deg.C.
Comparative example 5
The raw materials and the mass fraction thereof are as follows:
the preparation process comprises the following steps:
step 1: adding polybutylene adipate glycol (Mn = 2000), diphenylmethane diisocyanate and 1, 4-butanediol into a dynamic mixer through a pouring metering system according to a formula mass ratio for rapid mixing, adding the mixed material into a zone 1 of a twin-screw granulation system with 14 temperature zones, adding quantitative dihydroxy polydimethylsiloxane into a zone 10 of the twin-screw granulation system to enable the R value of TPU to reach 1.01, and carrying out underwater granulation to obtain reactive hydroxy organosilicon modified TPU particles;
step 2: step 1: the obtained reactive hydroxyl organic silicon modified TPU particles are mixed with triaryl siloxane in a mixing machine to generate a crosslinking reaction, and the organic silicon modified crosslinking TPU is prepared.
The TPU samples from the above examples and comparative examples were tested according to the TPU performance test methods and the results are shown in table 1:
TABLE 1 comparison of Performance between examples and comparative examples
As can be seen from Table 1, the use of the compounded chain extender in the present invention can improve the mechanical strength and processability of the TPU; the organic silicon modifier is added in the TPU twin-screw granulation link, so that the strength loss caused by secondary processing of the TPU can be effectively avoided; the effect of the photoinitiator on the surface glossiness and the wear resistance of the TPU is obviously better than that of a peroxide initiator.
In conclusion, the reactive organic silicon modifier is introduced into the TPU, and then the crosslinking reaction is carried out under the action of the photoinitiator, so that the prepared organic silicon modified crosslinked TPU is easy to process and has excellent wear resistance and mechanical property; the production process is simple and easy to implement, and can be widely applied to the fields of shoe materials, industrial trundles, sealing elements and the like.
Claims (10)
1. An organosilicon modified wear-resistant TPU is characterized by being prepared from the following substances in percentage by mass:
wherein:
the sum of the mass fractions of the polymer polyol, the diisocyanate and the chain extender is 100 percent, and the mass fractions of the organic silicon modifier and the initiator are the proportion on the basis;
the initiator is a cationic photoinitiator, and the cationic luminous initiator is triarylsiloxane.
2. The organosilicon modified abrasion resistant TPU of claim 1, wherein said polymer polyol is one or more of poly (ethylene glycol adipate) diol, poly (butylene glycol adipate) diol, poly (hexamethylene glycol adipate) diol, poly (ethylene glycol adipate-butylene glycol) diol, poly (butylene glycol adipate-adipate) diol, poly (butylene glycol sebacate) diol, poly (hexamethylene glycol sebacate) diol, or poly (ethylene glycol sebacate) diol.
3. The silicone modified abrasion resistant TPU of claim 1 wherein said diisocyanate is one of diphenylmethane diisocyanate, p-phenylene diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 1, 4-cyclohexyl-diisocyanate or decane-1, 10-diisocyanate.
4. The organosilicon modified wear-resistant TPU of claim 1, wherein the chain extender is a compound of chain extender 1 and chain extender 2, and the chain extender 1 is one or more of ethylene glycol, propylene glycol, 1, 4-butanediol, 1, 6-hexanediol, and methyl propylene glycol.
5. The silicone modified abrasion resistant TPU of claim 4 wherein said chain extender 2 is trimethylolpropane.
6. The silicone modified abrasion resistant TPU of claim 1 wherein the silicone modifier is a reactive hydroxysilicone modifier.
7. A method of making the silicone modified abrasion resistant TPU of any of claims 1 to 6 comprising the steps of:
(1) Adding polymer polyol, diisocyanate and a chain extender into a dynamic mixer through a pouring metering system according to the formula mass ratio, mixing, adding the mixed material into a zone 1 of a twin-screw granulation system with fourteen temperature zones, keeping the temperature of twin screws at 140-220 ℃, adding a quantitative organic silicon modifier into a zone 10 of the twin-screw granulation system, reacting, and carrying out underwater granulation to obtain reactive hydroxyl organic silicon modified TPU (TPU) particles;
(2) And (2) mixing the reactive hydroxyl organic silicon modified TPU particles obtained in the step (1) with an initiator in a mixer to perform a crosslinking reaction to prepare the organic silicon modified wear-resistant TPU.
8. The method for preparing the organosilicon modified abrasion-resistant TPU according to claim 7, wherein the screw speed in step (1) is from 180 to 220rmp.
9. The method of preparing the silicone modified abrasion resistant TPU of claim 7 wherein the twin screw temperature set in step (1) is:
region 1-3: 160-180 ℃;
zone 4-10: 180-220 ℃;
11-14 region: 140-160 ℃;
underwater pelletizing temperature: 160-180 ℃.
10. Use of the silicone modified abrasion resistant TPU of any of claims 1-6 in shoe products, casters, seals.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202211472100.5A CN115716902A (en) | 2022-11-23 | 2022-11-23 | Organic silicon modified wear-resistant TPU (thermoplastic polyurethane), and preparation method and application thereof |
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| CN202211472100.5A CN115716902A (en) | 2022-11-23 | 2022-11-23 | Organic silicon modified wear-resistant TPU (thermoplastic polyurethane), and preparation method and application thereof |
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