CN115449214A

CN115449214A - Material for paddle and preparation method thereof

Info

Publication number: CN115449214A
Application number: CN202211244405.0A
Authority: CN
Inventors: 黄明娟
Original assignee: Shenzhen Aikang Sporting Goods Co ltd
Current assignee: Shenzhen Aikang Sporting Goods Co ltd
Priority date: 2022-10-12
Filing date: 2022-10-12
Publication date: 2022-12-09

Abstract

The application relates to a material for a paddle and a preparation method thereof, belonging to the technical field of paddle design; the paint comprises the following components in parts by mass: 150-250 parts of modified glass fiber; 100-160 parts of carbon fiber; 1200-1340 parts of thermoplastic elastic resin; 30-35 parts of a curing agent; 25-27 parts of an antioxidant; the thermoplastic elastomer resin comprises the following components: hydroxyl-terminated polybutadiene rubber, hydroxyl-terminated carboxypolyelastomers, toluene diisocyanate, a chain extender, a catalyst and anhydrous ferric chloride. According to the method, the modified glass fiber and the carbon fiber are added into the paddle material, so that the bonding performance between paddle material systems is enhanced; the thermoplastic elastic resin is added, and the thermoplastic elastic resin has good mechanical property, so that the integral mechanical strength of the system is further improved.

Description

Material for paddle and preparation method thereof

Technical Field

The application relates to the field of paddles, in particular to a material for a paddle and a preparation method thereof.

Background

A paddle is a rowing tool. The upper end of the handle is a round rod which is convenient to hold by hand, so that the handle is called; the lower end is plate-shaped, namely a paddle board, which is used for water stirring, and the boat is advanced by utilizing Newton's third law in physics and through the reaction force of water waves.

The quant is in the use, and when the quant was scratched backward, the quant was to the backward thrust of water, and water is to the forward thrust of ship, but, the quant is after using for a long time, because constantly atress, mechanical properties descends, takes place deformation very easily for the fatigue degree of quant is too high, thereby appears buckling, cracked phenomenon, influences the use of quant.

Disclosure of Invention

In order to improve the mechanical property of the paddle material, the application provides a material for a paddle and a preparation method thereof.

In a first aspect, the present application provides a material for a paddle, which adopts the following technical scheme:

a material for a paddle comprises the following components in parts by mass:

150-250 parts of modified glass fiber; 100-160 parts of carbon fiber; 1200-1340 parts of thermoplastic elastic resin; 30-35 parts of a curing agent; 25-27 parts of an antioxidant;

the thermoplastic elastomer resin comprises the following components:

hydroxyl-terminated polybutadiene rubber, hydroxyl-terminated carboxypolyelastomers, toluene diisocyanate, a chain extender, a catalyst and anhydrous ferric chloride.

By adopting the technical scheme, the modified glass fiber and the carbon fiber are added into the paddle material, so that the bonding strength between the paddle materials can be improved, the bonding performance between paddle material systems can be enhanced, and the mechanical property of the paddle material can be improved; in the thermoplastic elastic resin, the hydroxyl-terminated polybutadiene rubber is a rubber containing hydroxyl and has good mechanical properties, the hydroxyl-terminated polybutadiene rubber forms a polyurethane elastomer after being cured and has a hard section and a soft section to form a soft-hard staggered polymer network, and the overall mechanical strength of the system is further improved; the paddle is aged after being used for a period of time, cracks can appear, the subsequent use condition of the paddle is influenced, the hydroxyl-terminated poly elastomer is introduced, the hydroxyl-terminated poly elastomer and iron ions in anhydrous ferric chloride are complexed to form a cross-linked network, the mechanical property of the thermoplastic elastic resin is further improved, and meanwhile, the self-repairing can be realized by introducing a metal coordination bond, so that the paddle material has self-healing capacity, and the service life of the paddle material is prolonged.

Preferably, the hydroxyl-terminated polybutadiene rubber is prepared by the following method:

mixing butadiene rubber and cyclohexane to obtain a solution A; mixing 3-chloroperoxybenzoic acid with tetrahydrofuran to obtain a 3-chloroperoxybenzoic acid solution; mixing periodic acid with tetrahydrofuran to obtain periodic acid solution; adding a 3-chloroperoxybenzoic acid solution into the solution A for reaction, then adding a periodic acid solution for reaction, adding sodium bicarbonate and an antioxidant after the reaction, mixing to obtain a mixture B, adding sodium borohydride and tetrahydrofuran into the mixture, drying after the reaction, and then filtering to remove impurities to obtain the hydroxyl-terminated polybutadiene rubber.

Preferably, the hydroxyl-terminated carboxypolyelastomer is prepared by the following method:

mixing sodium bromate, sodium bisulfate, tetrahydrofuran, deionized water and hydroxyl-terminated polybutadiene rubber to obtain a mixed solution C; and adding acetonitrile into the mixed solution C, then adding magnesium sulfate, standing, and performing suction filtration to obtain the hydroxyl-terminated carboxypolymethylene.

Preferably, the thermoplastic elastomer resin is prepared by the following method:

drying the hydroxyl-terminated polybutadiene rubber, adding tetrahydrofuran and toluene diisocyanate to obtain a mixture D, and adding the catalyst into the mixture D to react to obtain a prepolymer; mixing the hydroxyl-terminated carboxypolyelastomers with tetrahydrofuran and anhydrous ferric chloride, and reacting to obtain a mixture E; and adding a chain extender into the obtained prepolymer to react with the prepared mixture E to obtain a complex elastomer, and drying to obtain the thermoplastic elastic resin.

Preferably, the mass ratio of the hydroxyl-terminated polybutadiene rubber, the hydroxyl-terminated carboxypolyelastomer, the toluene diisocyanate and the anhydrous ferric chloride is 1.4 (0.3-0.35) to (0.15-0.17).

By adopting the technical scheme, the mass ratio of the hydroxyl-terminated polybutadiene rubber, the hydroxyl-terminated carboxypolyelastomer, the toluene diisocyanate and the anhydrous ferric chloride is controlled within the range, and the thermoplastic elastic resin with more excellent performance can be obtained.

Preferably, the glass modified fiber comprises cyanoethyl triacetoxy silane and glass fiber.

Through adopting above-mentioned technical scheme, use and draw together cyanoethyl triacetoxy silane to carry out modification to glass fiber, can promote the combination effect between glass fiber and the thermoplastic elastic resin, reduce the debonding phenomenon that two-phase interface appears to reduced the cracked condition of glass fiber organism, further promoted glass fiber's intensity, thereby strengthened the holistic mechanical strength of quant material.

Preferably, the modified glass fiber is prepared by the following method:

mixing cyanoethyl trichlorosilane with acetic anhydride, reacting, and removing acetyl chloride to obtain cyanoethyl triacetoxy silane; heating the glass fiber to obtain pretreated glass fiber; adding the cyanoethyl triacetoxy silane into deionized water for reaction to obtain a hydrolyzed silanol solution, mixing and soaking the obtained pretreated glass fiber and the silanol solution, filtering the silanol solution, washing and drying to obtain the modified glass fiber.

By adopting the technical scheme, the cyanoethyl triacetoxy silane forms silanol after hydrolysis, the silanol hydroxyl has strong reactivity, and can easily react with the hydroxyl on the surface of the glass fiber, so that the silanol hydroxyl and the surface of the glass fiber form firm chemical combination, and the overall mechanical property of the paddle material is improved.

Preferably, the mass fraction of the cyanoethyl triacetoxysilane in the aqueous solution of cyanoethyl triacetoxysilane is 0.45% to 0.55%.

By adopting the technical scheme, the mass fraction of the cyanoethyl triacetoxysilane in the cyanoethyl triacetoxysilane aqueous solution is controlled within the range, and the modified glass fiber with better performance can be obtained.

Preferably, the catalyst is dibutyltin dilaurate.

In a second aspect, the present application provides a method for preparing a paddle material, which adopts the following technical scheme:

a preparation method for a paddle material comprises the following steps:

pouring thermoplastic elastic resin into the core film, adding divinyl triamine for primary curing, and demolding to obtain a core material; mixing the modified glass fiber and the carbon fiber to obtain a mixed fiber, and including the mixed fiber outside the core material to obtain a prefabricated body; and (3) putting the prefabricated body into a forming die, filling the remaining gaps of the die with thermoplastic elastic resin, an antioxidant and diethylenetriamine, curing and forming, and demolding to obtain the paddle material.

In summary, the present application includes at least one of the following beneficial technical effects:

1. the modified glass fiber is beneficial to improving the bonding strength between the thermoplastic elastic resin and the fiber, the bonding strength between propeller material systems is improved, and the mechanical property of the propeller material is improved; the hydroxyl-terminated polybutadiene rubber is rubber containing hydroxyl and has good mechanical property, the hydroxyl-terminated polybutadiene rubber forms a polyurethane elastomer after being cured, and has a hard section and a soft section to form a soft-hard staggered polymer network, so that the overall mechanical strength of the system is further improved; meanwhile, the hydroxyl-terminated carboxypolyelastomers are introduced, and are complexed with iron ions in anhydrous ferric chloride to form a cross-linked network, so that the mechanical property of the thermoplastic elastic resin is further improved, and meanwhile, the self-repairing can be realized by introducing metal coordination bonds, so that the propeller material has self-healing capability, and the service life of the propeller material is prolonged;

2. the cyanoethyl triaminoxysilane forms silanol after hydrolysis, silanol hydroxyl has strong activity, and can easily react with hydroxyl on the surface of the glass fiber, so that firm chemical combination can be formed on the surface of the glass fiber, the combination effect between the glass fiber and the thermoplastic elastic resin is improved, the debonding phenomenon of a two-phase interface is reduced, the situation that a glass fiber organism is broken is reduced, the strength of the glass fiber is further improved, and the overall mechanical strength of the paddle material is enhanced.

Detailed Description

The embodiment of the application discloses a material for a paddle and a preparation method thereof, and the application is further described in detail by combining the embodiment.

Example 1

Preparation of cyanoethyl triamidoxysilane:

adding 25g of cyanoethyl trichlorosilane and 80g of acetic anhydride into a reaction kettle, heating to 65 ℃, stirring for reaction for 7 hours, evaporating generated acetyl chloride in a manner of reaction and extraction at the same time in the reaction process, then distilling residual acetyl chloride under reduced pressure, controlling the pressure to be 0.1MPa, and distilling unreacted acetic anhydride at 55 ℃ to obtain the cyanoethyl triacetoxy silane.

Preparing modified glass fiber:

weighing 800g of glass fiber, and performing high-temperature treatment at 400 ℃ for 2h to remove impurities attached to the surface of the glass fiber to obtain pretreated glass fiber; adding 9g of cyanoethyl triacetoxysilane into 1991g of deionized water, controlling the stirring speed at 200r/min, reacting at 60 ℃ for 2h to obtain a hydrolyzed silanol solution, then adding the pretreated glass fiber into the silanol solution, controlling the temperature at 80 ℃, soaking for 3h, filtering out the silanol solution, washing the silanol residual solution on the surface of the pretreated glass fiber with ethanol, and then drying in a vacuum drying oven at 80 ℃ for 3h to obtain the modified glass fiber.

Preparation of hydroxyl-terminated polybutadiene rubber:

adding 700g of butadiene rubber into 6L of cyclohexane, and controlling the temperature at 35 ℃ until the butadiene rubber is completely dissolved to obtain a solution A; adding 80g of 3-chloroperoxybenzoic acid into 1.5L of tetrahydrofuran to obtain a 3-chloroperoxybenzoic acid solution; adding 80g of periodic acid into 1.5L of tetrahydrofuran to obtain a periodic acid solution; adding a 3-chloroperoxybenzoic acid solution into the solution A for reaction for 3 hours, adding a periodic acid solution for reaction for 4 hours, adding 20g of sodium bicarbonate and 20g of antioxidant after the reaction is finished, uniformly stirring to obtain a mixture B, standing the mixture B for 12 hours, adding 200g of sodium borohydride and 3L of tetrahydrofuran, reacting for 4 hours at the temperature of 30 ℃, adding deionized water to quench excessive sodium borohydride after the reaction is finished, adding anhydrous magnesium sulfate for drying after no bubble is generated in the system, filtering to remove impurities, and performing rotary evaporation to obtain hydroxyl-terminated polybutadiene rubber; wherein the antioxidant is 2, 6-di-tert-butyl-4-methylphenol (CAS number: 128-37-0).

Preparation of a hydroxyl terminated carboxypolyelastomer:

mixing 50g of sodium bromate, 50g of sodium bisulfate, 600g of tetrahydrofuran and 600g of deionized water with 33g of the prepared hydroxyl-terminated polybutadiene rubber to obtain a mixed solution C; adding 2000g of acetonitrile into the mixed solution C, refluxing for 60min at 55 ℃, adding 400g of magnesium sulfate after the reflux is finished, standing for 2h, performing suction filtration, and performing rotary evaporation to obtain the hydroxyl-terminated carboxyl poly-elastomer.

Preparing a thermoplastic elastic resin:

vacuum drying 700g of the prepared hydroxyl-terminated polybutadiene rubber at the temperature of 120 ℃ for 6h, cooling to 25 ℃, adding 2L of tetrahydrofuran and 150g of toluene diisocyanate to obtain a mixture D, adding 10g of a catalyst to the mixture D, and reacting at the temperature of 25 ℃ for 3h to obtain a prepolymer; dissolving 500g of the prepared hydroxyl-terminated carboxyl poly elastomer in 480ml of tetrahydrofuran, adding 85g of anhydrous ferric chloride, and reacting for 1.5h at 25 ℃ to obtain a mixture E; adding 35g of chain extender into the obtained prepolymer to react with the prepared mixture E for 1h at 25 ℃, then volatilizing the solvent in a blast drying oven at 30 ℃ for 7h to obtain a complex elastomer, and finally adding the complex elastomer into a vacuum drying oven at 75 ℃ for drying for 18h to obtain the thermoplastic elastic resin; wherein the catalyst is dibutyltin dilaurate; the chain extender is 1, 4-butanediol.

Preparing a paddle material:

pouring 300g of the prepared thermoplastic elastic resin into a core film, adding 19g of divinyl triamine at the temperature of 110 ℃ for primary curing, and demolding to obtain a core material; mixing 150g of the prepared modified glass fiber with 100g of carbon fiber to obtain a mixed fiber, and including the mixed fiber outside a core material to obtain a preform; putting the prefabricated body into a forming die, filling the remaining gap of the die with 1000g of the prepared thermoplastic elastic resin, 16g of the prepared antioxidant and 25g of the prepared divinyl triamine, controlling the pressure to be 0.15MPa, curing and forming at the temperature of 130 ℃, and demoulding to obtain the paddle material; wherein the antioxidant is 2, 6-di-tert-butyl-4-methylphenol (CAS number: 128-37-0).

Example 2

Preparation of cyanoethyl triamidoxysilane:

adding 35g of cyanoethyl trichlorosilane and 90g of acetic anhydride into a reaction kettle, heating to 75 ℃, stirring for reaction for 5 hours, evaporating generated acetyl chloride in a manner of reaction and extraction at the same time in the reaction process, then distilling residual acetyl chloride under reduced pressure, controlling the pressure to be 0.1MPa, and distilling unreacted acetic anhydride at 55 ℃ to obtain the cyanoethyl triacetoxy silane.

Preparing modified glass fiber:

weighing 1000g of glass fiber, and performing high-temperature treatment at 400 ℃ for 2h to remove impurities attached to the surface of the glass fiber to obtain pretreated glass fiber; adding 16.5g of cyanoethyl triacetoxysilane into 2983.5g of deionized water, controlling the stirring speed at 200r/min, reacting at 60 ℃ for 2h to obtain a hydrolyzed silanol solution, then adding the pretreated glass fiber into the silanol solution, controlling the temperature at 80 ℃, soaking for 3h, filtering out the silanol solution, washing the silanol residual solution on the surface of the pretreated glass fiber with ethanol, and then putting the solution into a vacuum drying oven at 80 ℃ for drying for 3h to obtain the modified glass fiber.

Preparation of hydroxyl-terminated polybutadiene rubber:

adding 800g of butadiene rubber into 6.8L of cyclohexane, and controlling the temperature at 37 ℃ until the butadiene rubber is completely dissolved to obtain a solution A; adding 100g of 3-chloroperoxybenzoic acid into 1.7 of tetrahydrofuran to obtain a 3-chloroperoxybenzoic acid solution; adding 100g of periodic acid into 1.7L of tetrahydrofuran to obtain a periodic acid solution; adding a 3-chloroperoxybenzoic acid solution into the solution A to react for 3 hours, adding a periodic acid solution to react for 4 hours, adding 24g of sodium bicarbonate and 24g of antioxidant after the reaction is finished, uniformly stirring to obtain a mixture B, standing the mixture B for 12 hours, adding 240g of sodium borohydride and 3.4L of tetrahydrofuran, reacting for 4 hours at the temperature of 30 ℃, adding deionized water to quench excessive sodium borohydride after the reaction is finished, adding anhydrous magnesium sulfate to dry after no bubble is generated in the system, filtering to remove impurities, and performing rotary evaporation to obtain the hydroxyl-terminated polybutadiene rubber; wherein the antioxidant is 2, 6-di-tert-butyl-4-methylphenol (CAS number: 128-37-0).

Preparation of hydroxyl-terminated carboxypolyelastomers:

mixing 54g of sodium bromate, 54g of sodium bisulfate, 650g of tetrahydrofuran and 650g of deionized water with 39g of the hydroxyl-terminated polybutadiene rubber to obtain a mixed solution C; adding 2200g of acetonitrile into the mixed solution C, refluxing for 60min at 65 ℃, adding 460g of magnesium sulfate after the refluxing is finished, standing for 2h, performing suction filtration, and performing rotary evaporation to obtain the hydroxyl terminated carboxyl poly-elastomer.

Preparing a thermoplastic elastic resin:

756g of the prepared hydroxyl-terminated polybutadiene rubber is dried in vacuum at the temperature of 120 ℃ for 6h, cooled to 25 ℃, added with 4L of tetrahydrofuran and 189g of toluene diisocyanate to obtain a mixture D, added with 24g of catalyst into the mixture D, and reacted at the temperature of 25 ℃ for 3h to obtain a prepolymer; dissolving 540g of the prepared hydroxyl-terminated carboxyl polymeric elastomer in 520ml of tetrahydrofuran, adding 81g of anhydrous ferric chloride, and reacting for 1.5h at 25 ℃ to obtain a mixture E; adding 42g of chain extender into the obtained prepolymer to react with the prepared mixture E for 1 hour at 25 ℃, then volatilizing the solvent in a blast drying oven at 30 ℃ for 7 hours to obtain a complex elastomer, and finally adding the complex elastomer into a vacuum drying oven at 75 ℃ for drying for 18 hours to obtain thermoplastic elastic resin; wherein the catalyst is dibutyltin dilaurate; the chain extender is 1, 4-butanediol.

Preparing a paddle material:

pouring 400g of the prepared thermoplastic elastic resin into a core film, adding 21g of diethylenetriamine at the temperature of 120 ℃ for primary curing, and demolding to obtain a core material; mixing 250g of the prepared modified glass fiber with 160g of carbon fiber to obtain a mixed fiber, and including the mixed fiber outside a core material to obtain a prefabricated body; putting the prefabricated body into a forming die, filling the residual gap of the die with 1200g of the prepared thermoplastic elastic resin, 18g of the prepared antioxidant and 27g of the prepared divinyl triamine, controlling the pressure to be 0.2MPa, curing and forming at the temperature of 140 ℃, and demolding to obtain the paddle material; wherein the antioxidant is 2, 6-di-tert-butyl-4-methylphenol (CAS number: 128-37-0).

Example 3

Preparation of cyanoethyl triacetoxy silane:

adding 30g of cyanoethyl trichlorosilane and 85g of acetic anhydride into a reaction kettle, heating to 65 ℃, stirring for reacting for 6 hours, evaporating generated acetyl chloride in a manner of reaction and extraction at the same time in the reaction process, then distilling residual acetyl chloride under reduced pressure, controlling the pressure to be 0.1MPa, and distilling unreacted acetic anhydride at 55 ℃ to obtain the cyanoethyl triacetoxy silane.

Preparing modified glass fiber:

weighing 900g of glass fiber, and performing high-temperature treatment at 400 ℃ for 2h to remove impurities attached to the surface of the glass fiber to obtain pretreated glass fiber; adding 12.5g of cyanoethyl triacetoxysilane into 2487.5g of deionized water, controlling the stirring speed at 200r/min, reacting at 60 ℃ for 2h to obtain a hydrolyzed silanol solution, then adding the pretreated glass fiber into the silanol solution, controlling the temperature at 80 ℃, soaking for 3h, filtering out the silanol solution, washing the silanol residue solution on the surface of the pretreated glass fiber by using ethanol, and then putting the solution into a vacuum drying oven at 80 ℃ for drying for 3h to obtain the modified glass fiber.

Preparation of hydroxyl-terminated polybutadiene rubber:

adding 320g of butadiene rubber into 6.4L of cyclohexane, and controlling the temperature at 36 ℃ until the butadiene rubber is completely dissolved to obtain a solution A; adding 90g of 3-chloroperoxybenzoic acid into 1.6L of tetrahydrofuran to obtain a 3-chloroperoxybenzoic acid solution; adding 90g of periodic acid into 1.6L of tetrahydrofuran to obtain a periodic acid solution; adding a 3-chloroperoxybenzoic acid solution into the solution A to react for 3 hours, adding a periodic acid solution to react for 4 hours, adding 22g of sodium bicarbonate and 22g of antioxidant after the reaction is finished, uniformly stirring to obtain a mixture B, standing the mixture B for 12 hours, adding 200g of sodium borohydride and 3.2L of tetrahydrofuran, reacting for 4 hours at the temperature of 30 ℃, adding deionized water to quench excessive sodium borohydride after the reaction is finished, adding anhydrous magnesium sulfate to dry after a system has no bubble, filtering to remove impurities, and performing rotary evaporation to obtain the hydroxyl-terminated polybutadiene rubber; wherein the antioxidant is 2, 6-di-tert-butyl-4-methylphenol (CAS number: 128-37-0).

Preparation of a hydroxyl terminated carboxypolyelastomer:

mixing 52g of sodium bromate, 52g of sodium bisulfate, 625g of tetrahydrofuran and 625g of deionized water with 36g of the prepared hydroxyl-terminated polybutadiene rubber to obtain a mixed solution C; adding 2100g of acetonitrile into the mixed solution C, refluxing for 60min at 60 ℃, adding 430g of magnesium sulfate after refluxing is finished, standing for 2h, performing suction filtration, and performing rotary evaporation to obtain the hydroxyl-terminated carboxypolyelastomer.

Preparing a thermoplastic elastic resin:

728g of the hydroxyl-terminated polybutadiene rubber is dried in vacuum at the temperature of 120 ℃ for 6h, after being cooled to 25 ℃, 3L of tetrahydrofuran and 171.6g of toluene diisocyanate are added to obtain a mixture D, 16.5g of catalyst is added to the mixture D, and the mixture D reacts at the temperature of 25 ℃ for 3h to obtain a prepolymer; dissolving 520g of the prepared hydroxyl-terminated carboxyl poly-elastomer in 500ml of tetrahydrofuran, adding 83.2g of anhydrous ferric chloride, and reacting at 25 ℃ for 1.5h to obtain a mixture E; adding 38.5g of chain extender into the obtained prepolymer to react with 74g of the prepared mixture E at 25 ℃ for 1h, then volatilizing the solvent in a forced air drying oven at 30 ℃ for 7h to obtain a complex elastomer, and finally adding the complex elastomer into a vacuum drying oven at 75 ℃ for drying for 18h to obtain the thermoplastic elastic resin; wherein the catalyst is dibutyltin dilaurate; the chain extender is 1, 4-butanediol.

Preparing a paddle material:

pouring 350g of the prepared thermoplastic elastic resin into a core film, adding 20g of divinyl triamine at the temperature of 115 ℃ for primary curing, and demolding to obtain a core material; mixing 200g of the prepared modified glass fiber with 130g of carbon fiber to obtain a mixed fiber, and including the mixed fiber outside a core material to obtain a prefabricated body; placing the prefabricated body into a forming die, filling the residual gap of the die with 1100g of the prepared thermoplastic elastic resin, 17g of antioxidant and 26g of divinyl triamine, controlling the pressure to be 0.17MPa, curing and forming at 135 ℃, and demolding to obtain the paddle material; wherein the antioxidant is 2, 6-di-tert-butyl-4-methylphenol (CAS number: 128-37-0).

Example 4

Example 4 based on example 3, example 4 differs from example 3 only in that: example 4 in preparing the modified glass fiber, 8.75g of cyanoethyl triacetoxy silane was weighed and 2491.25g of deionized water was weighed.

Example 5

Example 5 based on example 3, example 5 differs from example 3 only in that: example 5 in preparing modified glass fibers, 16.25g cyanoethyltrisiloxysilane was weighed and 2483.75g deionized water was weighed.

Example 6

Example 6 based on example 3, example 6 differs from example 3 only in that: example 6 in the preparation of a thermoplastic elastomer resin, 762.29g of a hydroxyl-terminated polybutadiene rubber was weighed, 544.49g of a hydroxyl-terminated carboxypolyelastomer was weighed, 108.89g of toluene diisocyanate was weighed, and 87.13g of anhydrous ferric chloride was weighed.

Example 7

Example 7 based on example 3, example 7 differs from example 3 only in that: example 7 in preparing the thermoplastic elastomer resin, 698.98g of the hydroxyl-terminated polybutadiene rubber was weighed, 499.27g of the hydroxyl-terminated carboxypolyelastomer was weighed, 224.67g of the toluene diisocyanate was weighed, and 79.88g of the anhydrous ferric chloride was weighed.

Example 8

Example 8 on the basis of example 3, example 8 differs from example 3 only in that: example 8 in the preparation of a thermoplastic elastomer resin, 743.43g of a hydroxyl-terminated polybutadiene rubber, 531.02g of a hydroxyl-terminated carboxypolyelastomer, 175.24g of toluene diisocyanate and 53.11g of anhydrous ferric chloride were weighed.

Example 9

Example 9 based on example 3, example 9 differs from example 3 only in that: example 9 in the preparation of a thermoplastic elastomer resin, 713.19g of a hydroxyl-terminated polybutadiene rubber was weighed, 509.42g of a hydroxyl-terminated carboxypolyelastomer was weighed, 168.11g of toluene diisocyanate was weighed, and 112.08g of anhydrous ferric chloride was weighed.

Comparative example 1

Comparative example 1 is based on example 3, the only difference between comparative example 1 and example 3 being: comparative example 1 in the preparation of the paddle material, the modified glass fibers were replaced with ordinary unmodified glass fibers.

Comparative example 2

Comparative example 2 is based on example 3, the only difference between comparative example 2 and example 3 being: comparative example 2 in preparing the thermoplastic elastomer resin, the hydroxyl terminated carboxypoly elastomer was replaced with a polyurethane elastomer.

Comparative example 3

Comparative example 3 based on example 3, comparative example 3 differs from example 3 only in that: comparative example 3 in the preparation of the thermoplastic elastomer resin, 770.67g of hydroxyl-terminated polybutadiene rubber, 550.48g of hydroxycarboxyl-terminated elastomer, 181.65g of toluene diisocyanate and 0g of anhydrous ferric chloride were weighed.

Performance test

The paddle materials of examples 1-9, comparative examples 1-3 were sampled and tested for the following properties:

mechanical Property test

Elastomer part 2 was molded and extruded with GB/T38273.2-2019 thermoplastic polyesters and polyethers: sample preparation and performance measurements "were standard, each sample was tested three times, and the test results were averaged and filled in table 1.

Self-repair performance test

Manufacturing a 20mm multiplied by 4mm multiplied by 2mm test piece from the prepared test sample, cutting a 15mm long and 1.5mm deep cut on the surface of the test piece by using a blade, then healing the test piece for 10 hours in a vacuum drying oven at 35 ℃, then performing a uniaxial tensile property test on the healed test piece by using a stretching machine, stretching under the conditions that the tensile deformation rate of a tensile machine of 100mm/min and the environmental temperature are 25 ℃, and calculating the tensile rate; the elongation is calculated as follows:

TABLE 1

As can be seen from Table 1, the tensile strength, the breaking strength and the elongation at break of the paddle materials prepared in the examples 1 to 3 are all above 10.00MPa, above 8.00MPa and above 180%, so that the paddle materials prepared in the application have good mechanical properties; the self-repairing rates of the examples 1 to 3 are all above 84.5, so that the oar material prepared by the method has good self-repairing capability.

As can be seen from table 1, example 4 differs from example 3 only in that: example 3 in the preparation of modified glass fiber, 12.5g of cyanoethyl triaminoxysilane, 2487.5g of deionized water, 8.75g of cyanoethyl triaminoxysilane, 2491.25g of deionized water, and example 4 compared with example 3, all of tensile strength, breaking strength and elongation at break were reduced because when the concentration of cyanoethyl triaminoxysilane was reduced, the number of silanol hydroxyl groups in the hydrolyzed silanol solution was reduced, and it was difficult to react with all of the hydroxyl groups on the glass fiber surface, so that hydrolyzed silanol was difficult to form firm chemical bonds with all of the glass fiber surface, and the effect of improving the mechanical properties of glass fiber was reduced, so the mechanical properties of the boat material in example 4 were reduced.

As can be seen from table 1, example 5 differs from example 3 only in that: example 5 in the preparation of modified glass fiber, 16.25g of cyanoethyl triaminoxysilane and 2483.75g of deionized water were weighed, and in example 5, compared with example 3, tensile strength, breaking strength and breaking elongation rate were all reduced because cyanoethyl triaminoxysilane in hydrolyzed silanol solution was too high in concentration and saturated, and cyanoethyl triaminoxysilane was subjected to polycondensation reaction, thereby reducing reactivity, weakening the bonding effect between hydroxyl groups in glass fiber and silanol hydroxyl groups, and reducing the mechanical property improvement effect on glass fiber, so that the mechanical property of the paddle material in example 5 was reduced.

As can be seen from table 1, example 6 differs from example 3 only in that: in example 3, when preparing a thermoplastic elastomer resin, 728g of hydroxyl-terminated polybutadiene rubber, 520g of hydroxyl-terminated carboxypolyelastomer, 171.6g of toluene diisocyanate, 83.2g of anhydrous ferric chloride, 762.29g of hydroxyl-terminated polybutadiene rubber weighed in example 6, 544.49g of hydroxyl-terminated polycarboelastomer, 108.89g of toluene diisocyanate, 87.13g of anhydrous ferric chloride, and in example 6, compared with example 3, the tensile strength and the breaking strength are reduced and the breaking elongation is increased, because the content of isocyanate groups is reduced and the polyurethane system is not completely crosslinked after the content of the toluene diisocyanate is reduced, so that the strength of the network structure formed in the system is reduced, the stability of the thermoplastic elastomer resin is reduced, the polyurethane resin is difficult to be effectively compounded with the modified glass fiber, and the coupling degree of the system is further reduced, so that the tensile strength and the breaking strength are reduced; after the crosslinking degree is reduced, the content of soft segments in the system is increased, so that the breaking elongation is increased.

As can be seen from table 1, example 7 differs from example 3 only in that: example 7 weighed 698.98g of hydroxyl-terminated polybutadiene rubber, 499.27g of hydroxyl-terminated carboxypolyelastomer, 224.67g of toluene diisocyanate and 79.88g of anhydrous ferric chloride; example 7 compared with example 3, tensile strength and breaking strength are increased and breaking elongation is reduced, because the content of the hydroxyl-terminated carboxyl poly elastomer in the system is too high after the proportion of the anhydrous ferric chloride is too small, so that ionic bonds in the system are too high, the soft segment content of the elastomer is reduced, and the breaking elongation is reduced; the crosslinking density of the system is too high, so that the tensile strength and the breaking strength are increased.

The self-repairing rate of the comparative example 7 is reduced, because the self-repairing performance of the comparative example 7 is reduced because the reduction of the soft segment content is not beneficial to the self-repairing of the system.

As can be seen from table 1, example 8 differs from example 3 only in that: example 8 weigh 743.43g of hydroxyl-terminated polybutadiene rubber, 531.02g of hydroxyl-terminated carboxypolyelastomer, 175.24g of toluene diisocyanate, and 53.11g of anhydrous ferric chloride; example 8 has a lower tensile strength and a lower breaking strength and an higher breaking elongation than example 3 because the proportion of anhydrous ferric chloride is lower and it is difficult to crosslink with all of the hydroxycarboxy polymer elastomer, the tensile strength and breaking strength of the thermoplastic elastomer resin are lower, and the hydroxycarboxy polymer elastomer and ferric chloride are difficult to completely crosslink, and thus the 1, 4-butanediol chain extender consumed is lower and the soft segment content in the system is higher, so that the breaking elongation of the whole system is improved.

The self-repairing rate of the embodiment 8 is reduced, because after the anhydrous ferric chloride content in the embodiment 8 is reduced, too many ionic bonds are introduced, the soft segment content of the elastomer is reduced, and the system is not beneficial to self-repairing, so that the self-repairing rate of the embodiment 8 is reduced.

As can be seen from table 1, example 9 differs from example 3 only in that: example 9 weighed 713.19g of hydroxyl-terminated polybutadiene rubber, 509.42g of hydroxyl-terminated carboxypolyelastomer, 168.11g of toluene diisocyanate and 112.08g of anhydrous ferric chloride; in example 9, compared with example 3, the tensile strength and the breaking strength are reduced, and the breaking elongation is increased, because the content of the anhydrous ferric chloride is too much, the hydroxyl-terminated polybutadiene rubber is over-cured, the soft segment content of the thermoplastic elastic resin is reduced, and the breaking elongation is reduced, meanwhile, due to the increase of the isocyanate group in the system, the hydrogen bond association between the rigid segments is caused, the crystallization in the system is increased, and the benzene ring in the toluene cyanate ester further reduces the flexibility of the system.

The self-repair rate of example 9 is decreased because the brittleness of the paddle material is increased after the curing of the system is excessive, and the elongation at break of the paddle material itself is decreased too much, which is not favorable for the self-repair of the paddle material, and thus the self-repair rate of example 9 is decreased.

As can be seen from table 1, in comparative example 1, when the modified glass fiber is replaced with the ordinary unmodified glass fiber when the paddle material is prepared, the compressive strength, the tensile strength and the elongation at break of comparative example 1 are all reduced, because the composite effect between the unmodified glass fiber and the thermoplastic elastic resin is reduced, and the phenomena of interfacial debonding, glass fiber matrix breaking and the like occur, so that the bonding effect of the whole paddle material is reduced, and therefore, the compressive strength, the tensile strength and the elongation at break of comparative example 1 are all reduced.

As can be seen from table 1, in comparative example 2, in the process of preparing the thermoplastic elastic resin, the hydroxy-terminated carboxypolyelastomer is replaced with the hydroxy-terminated polybutadiene rubber, the compressive strength, the tensile strength and the elongation at break of comparative example 2 are all reduced, because the anhydrous ferric chloride in comparative example 2 cannot be crosslinked and thus it is difficult to form a stable network structure, the bonding effect of the thermoplastic elastic resin as a whole is reduced, the coupling strength of the system is reduced, and the mechanical properties of comparative example 2 are reduced.

The self-healing efficiency of comparative example 2 is decreased because the cross-linking effect of the metal coordination bond in ferric chloride is reduced, so that the self-healing effect of the propeller system is decreased, and thus the self-healing performance of comparative example 2 is decreased.

As is apparent from Table 1, in comparative example 3, when the thermoplastic elastomer resin was prepared, the compressive strength, tensile strength and elongation at break of comparative example 3 were reduced without adding anhydrous ferric chloride, because the hydroxycarboxy-terminated elastomer in comparative example 3 was difficult to crosslink and form a stable network structure, and the mechanical properties of comparative example 3 were reduced because the brittleness of the entire thermoplastic elastomer resin was increased due to the introduction of too many ionic bonds.

The self-repairing rate of the comparative example 3 is reduced because the self-repairing effect is difficult to achieve due to the fact that the polymerization network formed by the paddle material is reduced without introducing the metal coordination bond, and the self-repairing rate of the comparative example 3 is reduced.

The present embodiment is merely illustrative and not restrictive, and various changes and modifications may be made by persons skilled in the art without departing from the scope of the present invention as defined in the appended claims. The technical scope of the present application is not limited to the contents of the specification, and must be determined according to the scope of the claims.

Claims

1. A material for a paddle, characterized by: the adhesive comprises the following components in parts by mass:

the thermoplastic elastic resin comprises the following components:

2. A material for a paddle according to claim 1 wherein: the hydroxyl-terminated polybutadiene rubber is prepared by the following method:

mixing butadiene rubber and cyclohexane to obtain a solution A; mixing 3-chloroperoxybenzoic acid with tetrahydrofuran to obtain a 3-chloroperoxybenzoic acid solution; mixing periodic acid with tetrahydrofuran to obtain periodic acid solution; adding a 3-chloroperoxybenzoic acid solution into the solution A for reaction, adding a periodic acid solution for reaction, adding sodium bicarbonate and an antioxidant after the reaction, mixing to obtain a mixture B, adding sodium borohydride and tetrahydrofuran into the mixture, drying after the reaction, and filtering to remove impurities to obtain the hydroxyl-terminated polybutadiene rubber.

3. A material for a paddle according to claim 2 wherein: the hydroxyl-terminated carboxypolymethylene elastomer is prepared by the following method:

4. A material for a paddle according to claim 2 wherein: the thermoplastic elastic resin is prepared by the following method:

5. A material for a paddle according to claim 1 wherein: the mass ratio of the hydroxyl-terminated polybutadiene rubber, the hydroxyl-terminated carboxypolyelastomer, the toluene diisocyanate and the anhydrous ferric chloride is 1.4 (0.3-0.35) to (0.15-0.17).

6. A material for a paddle according to claim 1 wherein: the glass modified fiber comprises cyanoethyl triacetoxy silane and glass fiber.

7. A material for a paddle according to claim 1 wherein: the modified glass fiber is prepared by the following method:

8. A material for a paddle according to claim 7 wherein: the mass fraction of the cyanoethyl triacetoxysilane in the cyanoethyl triacetoxysilane aqueous solution is 0.45-0.55%.

9. A material for a paddle according to claim 1 wherein: the catalyst is dibutyltin dilaurate.

10. A method for preparing a material for a paddle is characterized by comprising the following steps: the method comprises the following steps:

pouring thermoplastic elastic resin into the core film, adding divinyl triamine for primary curing, and demolding to obtain a core material; mixing the modified glass fiber and the carbon fiber to obtain a mixed fiber, and including the mixed fiber outside the core material to obtain a prefabricated body; and (3) putting the prefabricated body into a forming die, filling the residual gap of the die with thermoplastic elastic resin, antioxidant and divinyl triamine, curing and forming, and demolding to obtain the paddle material.