CN109337040B - Thermoplastic polyurethane colloidal particles for toothbrush bristles and preparation thereof - Google Patents
Thermoplastic polyurethane colloidal particles for toothbrush bristles and preparation thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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Abstract
The invention discloses thermoplastic polyurethane colloidal particles for toothbrush bristles and a preparation method thereof, wherein the thermoplastic polyurethane colloidal particles are prepared from the following raw materials in parts by weight: polytetrahydrofuran ether glycol, diphenylmethane diisocyanate, a chain extender and an auxiliary agent; wherein the molecular weight of the polytetrahydrofuran ether glycol is 2000-4000, the molecular weight of the thermoplastic polyurethane colloidal particles is 50000-120000, and the chain extender is prepared from 1, 4-butanediol: 2-methyl-1, 3-propanediol: 1, 3-butanediol: 3.5 to 8.5 percent of trimethylolpropane: 0.5% -3.5%: 0.2% -0.7%: 0.2 to 0.7 percent of the total weight of the components. The toothbrush bristles produced by using the thermoplastic polyurethane granules have the advantages of easy demoulding, no handle drop, no hair breakage, high yield, quality stability guarantee and the like.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to thermoplastic polyurethane rubber particles for toothbrush bristles and a preparation method thereof.
Background
The common toothbrush bristles are mostly made of PBT (polybutylene terephthalate) and nylon, are mostly formed by weaving and are not formed by injection molding, and have the defects of large bristle diameter, low density, softness, poor elasticity and outward dispersion of bristle deformation after long-term use. The toothbrush bristles injection-molded by TPU have small bristle diameter, high density, softness and good elasticity, are not easy to deform after long-term use, and can maintain the original shape, so as to overcome the defects of the original material.
The prior TPU toothbrush hair products in the market mostly adopt polyester polyol in the formula, and have the defects of no hydrolysis resistance, hydrolysis and physical degradation of the toothbrush hair after long-term use, and no elastic deformation or even breakage of the toothbrush hair. If the anti-hydrolysis agent is added, the anti-hydrolysis agent is only short-acting and cannot ensure long-term use time, and the anti-hydrolysis agent cannot ensure no harm to human bodies. Another disadvantage is that it is not antibacterial, and the bristles of toothbrush are easy to breed bacteria and poison human body, so it is necessary to add antibacterial agent, which not only increases the cost, but also is short-lived and does not guarantee itself to be harmless to human body.
The existing TPU toothbrush hair injection molding technology can cause the problems of incapability of demolding, handle falling and easy hair breakage when the TPU is used alone, so a large amount of release agent needs to be added for production, but even if the release agent is added, the problems of unstable production, extremely high reject ratio and the like caused by the problems of uneven stirring, slipping of a binding rod of an injection molding machine and the like are caused, and the TPU toothbrush hair cannot be produced in some complex molds. In addition, because most of the existing TPU materials use polyester polyol with the molecular weight of less than 3000 or polyether polyol with the molecular weight of less than 2000 to improve the fluidity, the problem of low crystallinity and slow setting of the TPU is caused, and the problems of stem removal and hair breakage are easily caused. There are problems associated with the use of polyether polyols having a molecular weight of 2000 or more for the preparation of TPU. Therefore, the mass production of transparent TPU particles produced with PTMG molecular weight greater than 2000 is essentially not used in the market at present.
The TPU material brush bristle with good elasticity, no bacteria, no hydrolysis, long-term use, fine brush bristle and high density is one of the best choices for providing effective oral cavity cleaning and long-term use. In the existing toothbrush production technology of TPU material bristles, the production is unstable due to the addition of a large amount of parting agent, and the TPU material uses low molecular weight polyalcohol to change and remove the handle, so that the problems of high handle removing rate, easy breakage, low yield and high reject ratio generally exist, and the production cost is overhigh and the quality is unstable. How to improve the product yield and quality stability without adding a mold release agent, without breaking the handle, and without breaking the bristles is one of the major research subjects of the current toothbrush production technology of TPU bristles.
Disclosure of Invention
The present invention has been made to overcome the above-mentioned disadvantages of the prior art, and an object of the present invention is to provide thermoplastic polyurethane rubber particles for toothbrush bristles and a method for preparing the same. The prepared thermoplastic polyurethane colloidal particles are used for injection molding of bristles of toothbrushes, can be added with no release agent, improve the defects of easy demoulding, easy handle release, easy hair breakage and the like in the prior art, improve the yield, ensure the quality stability, and are used for producing excellent toothbrushes which are not hydrolyzed, antibacterial, anti-UV, good in elasticity, not deformed for a long time and high in efficiency for cleaning oral cavities.
In order to solve the technical problems, the invention provides the following technical scheme:
a thermoplastic polyurethane colloidal particle for toothbrush bristles is prepared from the following raw materials in parts by weight:
the molecular weight of the polytetrahydrofuran ether glycol is 2000-4000, the molecular weight of the thermoplastic polyurethane colloidal particles is 50000-120000, and the weight ratio of the chain extender is as follows:
preferably, the weight ratio of the chain extender is as follows:
the thermoplastic polyurethane (TPU for short) is prepared by using polyester polyol with the molecular weight of below 3000 or polyether polyol with the molecular weight of below 2000, and the problems of low crystallinity and slow setting of the TPU exist, so that the produced toothbrush is easy to have the problems of handle removal and hair breakage. When the polyether glycol with the molecular weight more than 2000 is used for preparing the TPU, the separation degree of a hard section and a soft section of the TPU can be increased, the shaping speed in the injection molding processing is increased, the tensile strength of the toothbrush bristles is rapidly improved, the bonding strength between the toothbrush bristles and a toothbrush handle is increased in the injection molding process, the problems of handle release and bristle breakage are solved, and the hydrolysis resistance and the antibacterial property of the toothbrush bristles are kept.
However, to use polyether polyol with molecular weight greater than 2000, and to select polytetrahydrofuran ether glycol (PTMG for short) to prepare TPU, two major problems need to be solved: first, since PTMG having a molecular weight of more than 2000 is used, the particle is opaque and milky due to phase separation, which is called pearl effect. Secondly, when the molecular weight of PTMG is larger than 2000, the initial reactivity with diphenylmethane diisocyanate (MDI for short) is slow, so that the synthetic reaction of TPU is not easy to control.
In order to solve the two problems, the invention particularly selects and mixes 1, 4-butanediol (BDO for short), 2-methyl-1, 3-propanediol (MPO for short), 1, 3-butanediol and trimethylolpropane (TMP for short) according to a proportion as the chain extender. The TPU is a block copolymer of a linear structure, the soft segment of which is made of PTMG, and the hard segment of which is made by reacting MDI with a chain extender, and BDO has a moderate carbon-carbon chain length, which enables the micro-domain orientation separation of the soft and hard segments, and better crystallinity of the hard segment of TPU, i.e., better orientation of the hard chain of TPU to be produced, so that the crystallization and orientation arrangement makes it easier to form hydrogen chains between polymer molecules, which means that it can produce better ordered crystallization, the rotation resistance of the crystals and the migration of the polymer segment, and finally shows that the polymer has excellent toughness and hardness. BDO has an extremely high reaction rate of hard segments due to its excellent chemical structure. However, when PTMG having a molecular weight of more than 2000 is used, the soft segment reaction rate of the TPU is low as a whole, and the hard segment reaction rate is relatively high, and an excessively high hard segment reaction rate causes an excessively high hard segment content, resulting in the occurrence of a pearl effect. At this time, MPO and 1, 3-butanediol are added to reduce the reaction rate of the hard segment, relatively increase the reaction rate of the soft segment, improve the pearl effect of the TPU prepared from PTMG with high molecular weight, and increase the transparency of the TPU, although one end hydroxyl of 1, 3-butanediol is secondary alcohol, the effect of eliminating the pearl effect is excellent, but the more the MPO and the 1, 3-butanediol are used, the lower the crystallinity is, and the slower the molding is. If too much 1, 3-butanediol is added, the reaction rate becomes too slow, which may affect the crystallization of TPU, assisted by the synthesis of MPO. Trihydroxyl TMP is added to form an excess star structure to increase the TPU forming speed.
However, the proper ratio of the components in the composite chain extender is difficult to determine. BDO is used as a main chain extender, and a large amount of white particles generated by TPU cannot be eliminated if the addition proportion is too large; too small a proportion of addition may lead to the final failure of the TPU to be shaped. MPO has 2 mutually symmetrical methyl groups as side groups, can affect the crystallinity of a hard segment to a certain extent but cannot damage the crystallinity, is a sharp instrument for assisting in adjusting the reaction rate, cannot play a role when added too little, but causes the problems of reduction of the mechanical property of TPU, poor swelling property, slow forming and the like when added too much to cause excessive influence. 1, 3-butanediol has a primary alcoholic hydroxyl group and a secondary alcoholic hydroxyl group, plays a crucial role in eliminating the pearl effect, and if the 1, 3-butanediol is added too much, the crystallinity of a hard segment is damaged too much, so that the TPU cannot be molded; if the amount of the compound is too small, the crystallinity is not sufficiently damaged, and the pearl effect cannot be eliminated. The TMP has three hydroxyl functions, so that the TPU can form a star-shaped structure, and blocks are connected to form, and the forming speed of the TPU is influenced if the TMP is added or not added; however, too much addition results in the formation of a cross-linked structure of the polymer, which becomes a thermosetting material and cannot be used for the production of toothbrush bristles. Repeated experiments and groping finally determine that the chain extender is prepared from 1, 4-butanediol: 2-methyl-1, 3-propanediol: 1, 3-butanediol: 3.5 to 8.5 percent of trimethylolpropane: 0.5% -3.5%: 0.2% -0.7%: 0.2% -0.7%, especially 7%: 2%: 0.5%: when 0.5 percent of the chain extender is mixed, the proportion reaches the best, and different functions of various chain extenders can be cooperated with each other, so that the thermoplastic TPU colloidal particles with excellent mechanical property and swelling property, transparency and no white particles are generated.
The TPU prepared by an ether preparation method by taking PTMG and MDI as raw materials has natural antibacterial effect.
When the formula proportion of the invention is used for synthesizing TPU, the balance of the gram equivalent of NCO-OH + functional groups can be controlled to correspond, the ratio of the two is close to 1, the NCO-is in slight excess, and the hardness is moderate at the moment. The small excess of NCO-contributes to crystallization forming and transparency, and can react with moisture and other free H +, so that the transparency and physical strength of the prepared TPU are further improved. Too low molecular weight of TPU results in poor physical properties and cannot be applied to bristle preparation; too large molecular weight results in poor flowability of the TPU, increased difficulty in subsequent processing and a substantial decrease in processability. The molecular weight of the TPU is controlled to be 50000-120000 most suitably, the molecular weight of the TPU is higher than that of a common TPU (the common TPU is 30000-80000 in general), the tensile strength and the breaking strength are stronger, the hardness and the elongation are better, and the TPU is more suitable for production of toothbrush bristles.
Preferably, the auxiliary agent comprises a release agent.
Preferably, the release agent is nanoscale ethylene bis stearamide, and the particle size is 100-500 nm.
Ethylene bis stearamide (EBS for short) is selected for external lubrication, has the best effect, and is also an external lubricant commonly used in TPU toothbrush production factories in the market at present. However, if the conventional EBS is directly added in the TPU production process to exert the effect, the using amount is as high as 2% -3%, so that the screw of the extruder for granulation is easy to slip and the production is unstable due to too large adding amount in the TPU production factory. Therefore, the external-slip EBS is added in the injection molding manufacturing process of a toothbrush production factory at present instead of being directly added in the TPU production process, and therefore, when the injection molding production of the toothbrush factory is carried out, the external-slip EBS is not uniformly dispersed, and a screw rod is easy to slip, so that the production is unstable, and the reject ratio is increased. To overcome this problem, the present invention employs nanoscale EBS to reduce the amount of additive usage and achieve the same slip effect. The nanometer EBS replaces the traditional mold release agent, greatly reduces the attraction between the fine toothbrush bristles and the mold, ensures easy demolding after injection molding and reduces the defective rate caused by broken bristles and deformation of the toothbrush bristles. The nano-scale EBS can greatly reduce the addition amount, and the particle size is preferably 100-500 nm. The micro nano EBS can not cause unstable factors in the production process, thereby ensuring the production stability and the product quality.
Preferably, the auxiliary agent further comprises one or more of an ultraviolet resistant agent and an antioxidant.
Preferably, the anti-ultraviolet agent is a mixture of benzotriazole and its derivatives and hindered amine compounds.
Ultraviolet radiation has a great destructive effect on high molecular materials. It destroys the weakest chemical bond in the high molecular compound to generate active free radical, and further can initiate a series of photo-oxidation degradation reactions to degrade the performance of the material until the use value is completely lost. Benzotriazole and its derivative can absorb most of ultraviolet radiation, convert the absorbed energy into harmless heat energy and release the harmless heat energy, can inhibit or delay the photooxidation degradation reaction, maintain the excellent performance of the material, and prolong the service life. The hindered amine is an organic amine compound with steric hindrance, has a good inhibition effect on the photo-oxidative degradation reaction of high polymers and organic compounds, has an action mechanism different from that of benzotriazole, inhibits the photo-oxidative degradation reaction by capturing free radicals, decomposing hydroperoxides, transferring energy of excited molecules and the like, and is a light stabilizer with excellent performance. The benzotriazole and hindered amine are mixed together to be used as the ultraviolet resistant agent, so that the ultraviolet resistant agent has the advantages of both, and can resist ultraviolet radiation in a synergistic manner, thereby greatly improving the light stability of TPU, and enabling the prepared toothbrush to have longer service life.
Preferably, the antioxidant is antioxidant 1010.
A preparation method of the thermoplastic polyurethane colloidal particles for the toothbrush bristle comprises the following steps:
A. adding polytetrahydrofuran ether glycol and diphenylmethane diisocyanate in proportion, and pre-stirring;
B. then adding the auxiliary agent according to the proportion, continuously stirring for a period of time, then adding the auxiliary agent according to the proportion, and continuously stirring;
C. and finally, adding the chain extender in proportion, and continuously stirring to generate thermoplastic polyurethane rubber particles.
Step A is used for producing the prepolymer, the auxiliary agent is added in step B to be beneficial to the uniform distribution of the auxiliary agent on each prepolymer, and then step C is used for chain extension polymerization of the prepolymer with the auxiliary agent, so that the uniform distribution of the auxiliary agent in the colloidal particles is ensured, and the quality of the colloidal particles is ensured.
Preferably, the temperature of the step A is 105-115 ℃; the temperature of the step B is 125-135 ℃; the temperature of the step C is 148-152 ℃.
Preferably, the stirring speed of the step A is controlled to be 1000 revolutions per minute, and the stirring time is 1.5 min; b, controlling the stirring speed in the step B to be 1500 rpm, and stirring for 2min every time an auxiliary agent is added; and the stirring speed of the step C is controlled at 3000 r/min.
The implementation of the invention has the following beneficial effects:
PTMG with molecular weight higher than 2000 is used as a raw material for synthesizing TPU, BDO, MPO, 1, 3-butanediol and TMP are finely configured and mixed according to a certain proportion to be used as a composite chain extender, the components play a synergistic effect, the two problems of difficult control of pearl effect and reaction are solved, and the prepared TPU has the advantages of hydrolysis resistance, antibiosis, no need of adding a release agent during injection molding, difficulty in handle removal and hair breakage and the like when being used for producing toothbrush bristles by matching with the use of nanoscale EBS.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below.
Example 1
A thermoplastic polyurethane colloidal particle for toothbrush bristles is prepared from the following raw materials in parts by weight:
wherein the molecular weight of the polytetrahydrofuran ether glycol is 2000.
The synthesis method comprises the following steps:
A. adding polytetrahydrofuran ether glycol and diphenylmethane diisocyanate in proportion, and pre-stirring;
B. then adding the auxiliary agent according to the proportion, and continuously stirring;
C. and finally, adding a chain extender in proportion, continuously stirring, keeping the molding temperature of the thermoplastic polyurethane colloidal particles at 150 ℃, and generating the thermoplastic polyurethane colloidal particles, wherein the molecular weight of the generated thermoplastic polyurethane colloidal particles is 50000-120000.
The toothbrush bristles produced by the TPU colloidal particles can be easily demoulded without adding a parting agent during injection molding, have high yield and stable quality, and have the advantages of hydrolysis resistance, antibiosis, good elasticity, difficult handle removal and hair breakage and the like.
Example 2
A thermoplastic polyurethane colloidal particle for toothbrush bristles is prepared from the following raw materials in parts by weight:
wherein the molecular weight of the polytetrahydrofuran ether glycol is 3000.
The synthesis method comprises the following steps:
A. adding polytetrahydrofuran ether glycol and diphenylmethane diisocyanate in proportion, and pre-stirring;
B. then adding the auxiliary agent according to the proportion, and continuously stirring;
C. and finally, adding a chain extender in proportion, continuously stirring, keeping the molding temperature of the thermoplastic polyurethane colloidal particles at 150 ℃, and generating the thermoplastic polyurethane colloidal particles, wherein the molecular weight of the generated thermoplastic polyurethane colloidal particles is 50000-120000.
The toothbrush bristles produced by the TPU colloidal particles can be easily demoulded without adding a parting agent during injection molding, have high yield and stable quality, and have the advantages of hydrolysis resistance, antibiosis, good elasticity, difficult handle removal and hair breakage and the like.
Example 3
A thermoplastic polyurethane colloidal particle for toothbrush bristles is prepared from the following raw materials in parts by weight:
wherein the molecular weight of the polytetrahydrofuran ether glycol is 3000.
The synthesis method comprises the following steps:
A. adding polytetrahydrofuran ether glycol and diphenylmethane diisocyanate in proportion, and pre-stirring;
B. then adding the auxiliary agent according to the proportion, and continuously stirring;
C. and finally, adding a chain extender in proportion, continuously stirring, keeping the molding temperature of the thermoplastic polyurethane colloidal particles at 150 ℃, and generating the thermoplastic polyurethane colloidal particles, wherein the molecular weight of the generated thermoplastic polyurethane colloidal particles is 50000-120000.
The toothbrush bristles produced by the TPU colloidal particles can be easily demoulded without adding a parting agent during injection molding, have high yield and stable quality, and have the advantages of hydrolysis resistance, antibiosis, good elasticity, difficult handle removal and hair breakage and the like.
Example 4
A thermoplastic polyurethane colloidal particle for toothbrush bristles is prepared from the following raw materials in parts by weight:
wherein the molecular weight of the polytetrahydrofuran ether glycol is 4000.
The synthesis method comprises the following steps:
A. adding polytetrahydrofuran ether glycol and diphenylmethane diisocyanate in proportion, and pre-stirring;
B. then adding the auxiliary agent according to the proportion, and continuously stirring;
C. and finally, adding a chain extender in proportion, continuously stirring, and keeping the molding temperature of the thermoplastic polyurethane colloidal particles at 150 ℃ to generate the thermoplastic polyurethane colloidal particles, wherein the molecular weight of the generated thermoplastic polyurethane colloidal particles is 50000-120000.
The toothbrush bristles produced by the TPU colloidal particles can be easily demoulded without adding a parting agent during injection molding, have high yield and stable quality, and have the advantages of hydrolysis resistance, antibiosis, good elasticity, difficult handle removal and hair breakage and the like.
Comparative example 1
The preparation of thermoplastic polyurethane rubber particles was carried out using the raw materials and the weight ratios as in example 3, except that only one chain extender BDO was used.
A thermoplastic polyurethane colloidal particle for toothbrush bristles is prepared from the following raw materials in parts by weight:
wherein the molecular weight of the polytetrahydrofuran ether glycol is 3000.
The synthesis method comprises the following steps:
A. adding polytetrahydrofuran ether glycol and diphenylmethane diisocyanate in proportion, and pre-stirring;
B. then adding the auxiliary agent according to the proportion, and continuously stirring;
C. and finally, adding the chain extender in proportion, continuously stirring, and keeping the molding temperature of the thermoplastic polyurethane colloidal particles at 150 ℃ to generate the thermoplastic polyurethane colloidal particles.
The TPU colloidal particles have a large amount of milky white particles, because BDO has proper carbon-carbon chain length and has no side chain, the BDO can quickly react with MDI, but because the used PTMG has the molecular weight of 3000, the reaction of the PTMG and the MDI becomes slow, namely the speed of a soft segment is reduced, the original reaction speed of a hard segment is too fast, the pearl effect is generated, the normal use of the TPU is influenced, and the TPU cannot be used for preparing bristles.
Comparative example 2
The preparation of thermoplastic polyurethane rubber particles was carried out using the raw materials and the weight ratios as in example 3, except that only one chain extender MPO was used.
A thermoplastic polyurethane colloidal particle for toothbrush bristles is prepared from the following raw materials in parts by weight:
wherein the molecular weight of the polytetrahydrofuran ether glycol is 3000.
The synthesis method comprises the following steps:
A. adding polytetrahydrofuran ether glycol and diphenylmethane diisocyanate in proportion, and pre-stirring;
B. then adding the auxiliary agent according to the proportion, and continuously stirring;
C. and finally, adding the chain extender in proportion, continuously stirring, and keeping the molding temperature of the thermoplastic polyurethane colloidal particles at 150 ℃ to generate the thermoplastic polyurethane colloidal particles.
The molded TPU crumb needs to be obtained after a longer wait. The molecular structure of MPO contains 2 methyl side groups which are symmetrical with each other, and the reaction forming speed is influenced. The incorporation of a large number of side groups (in this example only MPO containing side groups) into the TPU reduces its orientational crystallinity, which leads to a reduction in mechanical properties and poor swelling properties. However, because two hydroxyl groups of MPO are still primary alcoholic hydroxyl groups, the formed TPU colloidal particles can be obtained after a long time of waiting, and the efficiency is only extremely low, which does not meet the requirements of industrial production. The toothbrush bristles produced by using the TPU colloidal particles are fragile and cannot be normally used. MPO is much less crystal-breaking than 1,3BG, but is better than 1,3BG in relative molding.
Comparative example 3
The preparation of thermoplastic polyurethane rubber particles was carried out using the raw materials and the weight ratios as in example 3, except that only one chain extender, 1, 3-butanediol, was used.
A thermoplastic polyurethane colloidal particle for toothbrush bristles is prepared from the following raw materials in parts by weight:
wherein the molecular weight of the polytetrahydrofuran ether glycol is 3000.
The synthesis method comprises the following steps:
A. adding polytetrahydrofuran ether glycol and diphenylmethane diisocyanate in proportion, and pre-stirring;
B. then adding the auxiliary agent according to the proportion, and continuously stirring;
C. and finally, adding the chain extender in proportion, continuously stirring, and keeping the molding temperature of the thermoplastic polyurethane colloidal particles at 150 ℃ to generate the thermoplastic polyurethane colloidal particles.
The TPU cannot be molded because, unlike two primary alcohol functional groups of BDO, 1, 3-butanediol has only one primary alcohol functional group and the other is a secondary alcohol functional group, resulting in almost complete destruction of the hard segment crystallinity, inability to crystallize and mold, and inability to be used in subsequent production when only 1, 3-butanediol is used as a chain extender.
Comparative example 4
The preparation of thermoplastic polyurethane rubber particles was carried out using the raw materials and weight ratios as in example 3, except that only one chain extender TMP was used.
A thermoplastic polyurethane colloidal particle for toothbrush bristles is prepared from the following raw materials in parts by weight:
wherein the molecular weight of the polytetrahydrofuran ether glycol is 3000.
The synthesis method comprises the following steps:
A. adding polytetrahydrofuran ether glycol and diphenylmethane diisocyanate in proportion, and pre-stirring;
B. then adding the auxiliary agent according to the proportion, and continuously stirring;
C. and finally, adding the chain extender in proportion, continuously stirring, and keeping the molding temperature of the thermoplastic polyurethane colloidal particles at 150 ℃ to generate the thermoplastic polyurethane colloidal particles.
The TPU cannot be made because TMP is a trifunctional group and can be block-connected to form, but only TMP used as a chain extender forms a cross-linked structure and forms too much a network structure, resulting in poor thermoplasticity of the resulting polymer, which becomes a thermosetting material rather than a thermoplastic material, and cannot be made into TPU, which cannot be used for bristle production.
Comparative example 5
The raw materials and weight ratios as in example 3 were selected for the preparation of thermoplastic polyurethane rubber particles, except that two chain extenders were used. BDO and 1, 3-butanediol are replaced by equal MPO, and two chain extenders BDO and MPO with larger addition amount are selected for carrying out a composite experiment.
A thermoplastic polyurethane colloidal particle for toothbrush bristles is prepared from the following raw materials in parts by weight:
wherein the molecular weight of the polytetrahydrofuran ether glycol is 3000.
The synthesis method comprises the following steps:
A. adding polytetrahydrofuran ether glycol and diphenylmethane diisocyanate in proportion, and pre-stirring;
B. then adding the auxiliary agent according to the proportion, and continuously stirring;
C. and finally, adding the chain extender in proportion, continuously stirring, and keeping the molding temperature of the thermoplastic polyurethane colloidal particles at 150 ℃ to generate the thermoplastic polyurethane colloidal particles.
The TPU colloidal particles have a small amount of milky white particles, only BDO and MPO are used as chain extenders to prepare the TPU, although MPO has two methyl groups as side groups to reduce the oriented crystallinity between macromolecules, only MPO and BDO are used, the damaged crystallinity is insufficient, the hard segment rate cannot be effectively reduced, the generated colloidal particles have a pearl effect, and a small amount of white particles exist. If the input proportion of MPO is increased, the problems of reduction of mechanical property of TPU, poor swelling property, slow forming and the like are caused, the normal generation of TPU is influenced, and the preparation of subsequent bristles is influenced.
Comparative example 6
The raw materials and weight ratio as in example 3 were selected for the preparation of thermoplastic polyurethane rubber particles, except that three chain extenders were used. Considering that 1, 3-butanediol and BDO are isomers of each other and have the least content, the same amount of BDO is used instead of 1, 3-butanediol, and three chain extenders BDO, MPO and TMP are used for a compounding experiment.
A thermoplastic polyurethane colloidal particle for toothbrush bristles is prepared from the following raw materials in parts by weight:
wherein the molecular weight of the polytetrahydrofuran ether glycol is 3000.
The synthesis method comprises the following steps:
A. adding polytetrahydrofuran ether glycol and diphenylmethane diisocyanate in proportion, and pre-stirring;
B. then adding the auxiliary agent according to the proportion, and continuously stirring;
C. and finally, adding the chain extender in proportion, continuously stirring, and keeping the molding temperature of the thermoplastic polyurethane colloidal particles at 150 ℃ to generate the thermoplastic polyurethane colloidal particles.
The TPU colloidal particles have trace milky white particles, and the composition of BDO instead of 1, 3-butanediol is used, so that the composite synergistic effect of the chain extender is not obvious. Although BDO and 1, 3-butanediol are isomers, two hydroxyl groups in BDO form primary alcohol, so that the hydroxyl group on one secondary alcohol cannot be utilized to reduce the reaction rate of a hard segment like 1, 3-butanediol, and the reaction rate of the hard segment can be increased. When the formula is used for synthesizing TPU, the reaction rate of a hard chain segment cannot be reduced to a reasonable range, so that a pearl effect is generated, and the preparation of subsequent bristles is influenced.
Comparative example 7
The preparation of thermoplastic polyurethane rubber particles was carried out using the starting materials and the weight ratios as in example 3, except that polytetrahydrofuran ether glycol having a molecular weight of 1000 was used.
A thermoplastic polyurethane colloidal particle for toothbrush bristles is prepared from the following raw materials in parts by weight:
wherein the molecular weight of the polytetrahydrofuran ether glycol is 1000.
The synthesis method comprises the following steps:
A. adding polytetrahydrofuran ether glycol and diphenylmethane diisocyanate in proportion, and pre-stirring;
B. then adding the auxiliary agent according to the proportion, and continuously stirring;
C. and finally, adding the chain extender in proportion, continuously stirring, and keeping the molding temperature of the thermoplastic polyurethane colloidal particles at 150 ℃ to generate the thermoplastic polyurethane colloidal particles.
The TPU colloidal particles have low crystallinity, slow setting, low hard segment content and extremely poor physical properties, so that the produced toothbrush is easy to have the problems of handle removal and broken bristles.
Comparative example 8
The raw materials and weight ratio as in example 3 were selected for the preparation of thermoplastic polyurethane rubber particles, except that micron-sized EBS with a particle size of 6-9 μm was used.
A thermoplastic polyurethane colloidal particle for toothbrush bristles is prepared from the following raw materials in parts by weight:
wherein the molecular weight of the polytetrahydrofuran ether glycol is 3000.
The synthesis method comprises the following steps:
A. adding polytetrahydrofuran ether glycol and diphenylmethane diisocyanate in proportion, and pre-stirring;
B. then adding the auxiliary agent according to the proportion, and continuously stirring;
C. and finally, adding a chain extender in proportion, continuously stirring, keeping the molding temperature of the thermoplastic polyurethane colloidal particles at 150 ℃, and generating the thermoplastic polyurethane colloidal particles, wherein the molecular weight of the generated thermoplastic polyurethane colloidal particles is 50000-120000.
The toothbrush bristles produced by the TPU colloidal particles cannot be smoothly demoulded without adding a release agent during injection molding. The demolding can be smoothly carried out after a large amount of parting agents are added, but the production is unstable due to the problems of uneven stirring, slipping of a binding rod of an injection molding machine and the like, and the problem that the toothbrush is easy to break due to extremely high reject ratio is caused.
Example 5
The physical properties of the thermoplastic polyurethane rubber particles produced in examples 1 to 4 and comparative examples 1 to 8 were measured, and the results are shown in the following table:
experiments prove that only the embodiment 1-4 using the formula of the invention has the optimum properties of hardness, tensile strength, elongation, crack hardness, colloidal particle state and the like, is suitable for producing toothbrush bristles, and can produce high-quality bristles which are small in diameter, high in density, soft, good in elasticity and not easy to deform after long-term use.
Example 6
The toothbrush was prepared using the thermoplastic polyurethane granules produced in examples 1 to 4, and the physical properties thereof were measured, and the results are shown in the following table:
while the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
Claims (8)
1. The thermoplastic polyurethane colloidal particles for the toothbrush bristles are characterized by comprising the following raw materials in parts by weight:
the molecular weight of the polytetrahydrofuran ether glycol is 2000-4000, the molecular weight of the thermoplastic polyurethane colloidal particles is 50000-120000, and the weight ratio of the chain extender is as follows:
the auxiliary agent comprises a release agent; the release agent is nano-scale ethylene bis stearamide, and the particle size is 100-500 nm.
2. The thermoplastic polyurethane capsule for toothbrush bristles according to claim 1, wherein the chain extender is prepared in the following weight ratio:
3. the thermoplastic polyurethane gel particles for toothbrush bristles according to claim 1, wherein the auxiliary further comprises one or more of an ultraviolet screening agent and an antioxidant.
4. The thermoplastic polyurethane capsule for toothbrush bristles according to claim 3, wherein the anti-ultraviolet agent is a mixture of benzotriazole and its derivatives with hindered amine compounds.
5. The thermoplastic polyurethane gel particles for toothbrush bristles according to claim 3, wherein the antioxidant is antioxidant 1010.
6. A method for preparing the thermoplastic polyurethane gel particles for toothbrush bristles according to any one of claims 1 to 5, comprising the steps of:
A. adding polytetrahydrofuran ether glycol and diphenylmethane diisocyanate in proportion, and pre-stirring;
B. then adding the auxiliary agent according to the proportion, continuously stirring for a period of time, then adding the auxiliary agent according to the proportion, and continuously stirring;
C. and finally, adding the chain extender in proportion, and continuously stirring to generate thermoplastic polyurethane rubber particles.
7. The thermoplastic polyurethane gel for toothbrush bristles according to claim 6, wherein the temperature of the step A is 105 to 115 ℃; the temperature of the step B is 125-135 ℃; the temperature of the step C is 148-152 ℃.
8. The thermoplastic polyurethane gel particles for toothbrush bristles according to claim 6, wherein the stirring rate of the step A is controlled to be 1000 rpm, and the stirring time is 1.5 min; b, controlling the stirring speed in the step B to be 1500 rpm, and stirring for 2min every time an auxiliary agent is added; and the stirring speed of the step C is controlled at 3000 r/min.
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|---|---|---|---|---|
| CN101423596A (en) * | 2008-11-10 | 2009-05-06 | 于龙洲 | Production formula of water resistant thermoplastic urethane resin |
| CN102516747A (en) * | 2011-12-09 | 2012-06-27 | 上海锦湖日丽塑料有限公司 | Thermoplastic elastomer composition of encapsulation PETG (poly(ethylene terephthalate) glycol) and preparation method thereof |
| CN103242644A (en) * | 2013-04-28 | 2013-08-14 | 杭州纳美科技有限公司 | Antibacterial polyurethane toothbrush and preparation method thereof |
| WO2016168043A1 (en) * | 2015-04-14 | 2016-10-20 | Resinate Materials Group, Inc. | Polyester polyols with increased clarity |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101423596A (en) * | 2008-11-10 | 2009-05-06 | 于龙洲 | Production formula of water resistant thermoplastic urethane resin |
| CN102516747A (en) * | 2011-12-09 | 2012-06-27 | 上海锦湖日丽塑料有限公司 | Thermoplastic elastomer composition of encapsulation PETG (poly(ethylene terephthalate) glycol) and preparation method thereof |
| CN103242644A (en) * | 2013-04-28 | 2013-08-14 | 杭州纳美科技有限公司 | Antibacterial polyurethane toothbrush and preparation method thereof |
| WO2016168043A1 (en) * | 2015-04-14 | 2016-10-20 | Resinate Materials Group, Inc. | Polyester polyols with increased clarity |
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