CN104151518B - Polyurethane sport knee-pad composition and method of making the same - Google Patents
Polyurethane sport knee-pad composition and method of making the same Download PDFInfo
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- CN104151518B CN104151518B CN201410396936.0A CN201410396936A CN104151518B CN 104151518 B CN104151518 B CN 104151518B CN 201410396936 A CN201410396936 A CN 201410396936A CN 104151518 B CN104151518 B CN 104151518B
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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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- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/40—High-molecular-weight compounds
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract
The present invention relates to a kind of polyurethane sport knee-pad composition and method of making the same, belong to urethane applied technical field.Polyurethane sport knee-pad composition of the present invention, be made up of component A and B component, the weight ratio of A, B component is 100: 30-60, wherein the raw material of component A is special polyether polyvalent alcohol, polyether polyol with high activity, polymer polyatomic alcohol, chainextender, suds-stabilizing agent, whipping agent, catalyzer, oxidation inhibitor, photostabilizer and solid filler, and the raw material of B component is polyether glycol, isocyanic ester and storage stabilizing agent.Polyurethane sport knee-pad composition of the present invention, has excellent antidetonation resiliency and motion comfortableness, compared with traditional protection tool, substantially increases protection effect; The present invention also provides its preparation method, first prepares component A and B component, and then A, B component are carried out mechanical or manual being mixed to evenly and injected aluminum knee-pad mould, and cost is low, is simple and easy to implement.
Description
Technical field
The present invention relates to a kind of polyurethane sport knee-pad composition and method of making the same, belong to urethane applied technical field.
Background technology
Knee is an extremely important position at the volley, is simultaneously again a vulnerable position of more fragile appearance, or one injured time extremely pain and recover slower position.Therefore, professional protection tool-knee-pad is needed during motion.Knee-pad generally refers to the piece of cloth material for the protection of people's knee, and in modern sport games, the use being specifically designed to the elbow protector for sports of Sports Field is more widely.The elbow protector for sports of traditional sense is generally thick felt material " knee-pad "; be merely able to reduce to a certain extent or avoid in moving process injured; effectively can not absorb dispersion for sporter's impact energy that knee is subject at the volley, thus make elbow protector for sports have certain limitation for the protection of sporter's knee.
Summary of the invention
The object of this invention is to provide a kind of polyurethane sport knee-pad composition, it has excellent antidetonation resiliency and motion comfortableness, compared with traditional protection tool, substantially increases protection effect; Invention also provides simple preparation method.
Polyurethane sport knee-pad composition of the present invention, is made up of component A and B component, and the weight ratio of A, B component is 100: 30-60, wherein:
(1) component A is made up of the component of following parts by weight:
Special polyether polyvalent alcohol: 50-85 part,
Polyether polyol with high activity: 5-30 part,
Polymer polyatomic alcohol: 5-30 part,
Chainextender: 0.1-1.5 part,
Suds-stabilizing agent: 0.1-1.5 part,
Whipping agent: 2.5-4.5 part,
Catalyzer: 0.1-2.5 part,
Oxidation inhibitor: 0.1-5.0 part,
Photostabilizer: 0.1-5.0 part,
Solid filler: 0.1-5.0 part;
The hydroxyl value of described special polyether polyvalent alcohol is 270 ~ 320mgKOH/g, functionality is 2.9 ~ 3.1, using two or more in propylene glycol, glycerol, glycol ether or TriMethylolPropane(TMP) as mixing initiator, by 1,2-propylene oxide ring-opening polymerization or obtain, mass content≤20% of its ethylene oxide with oxyethane copolymerization;
(2) B component is made up of the component of following parts by weight:
Polyether glycol: 20-60 part,
Isocyanic ester: 40-80 part,
Storage stabilizing agent: account for 0.001% of B component gross weight.
Described special polyether polyvalent alcohol is used in polyurethane composition of the present invention, prepared polyurethane sport knee-pad goods have excellent antidetonation resiliency and motion comfortableness, after External Force Acting, noresidue is out of shape, and also has the excellent property such as low-temperature flexibility, buffering, sound insulation, sealing in addition.
Preferred proportion of primary OH groups >=70% of polyether polyol with high activity in described component A, number-average molecular weight is 4000 ~ 8000, with one or more in glycerol, trolamine or TriMethylolPropane(TMP) for initiator, with the polyoxytrimethylene trivalent alcohol of ethylene oxide-capped.Polyether polyol with high activity is used in polyurethane composition of the present invention, and prepared polyurethane sport knee-pad goods have the advantage that activity is high, demould time is short, effectively can improve the load, rebound resilience etc. of polyurethane product.
In described component A, polymer polyatomic alcohol belongs to organic filled polyol, for the production of high-mechanic or high-modulus is soft or semi-hard polyurethane foam plastic goods.By adding this kind of organic filling polyethers, can the low and porous plastics that load is high of production density, not only reached hardness requirement but also conservation.Polymer polyatomic alcohol be preferably Shandong blue star Dong great chemical company produce POP36/28, POP93/28 or HPOP40 in one or more.
In described component A, chainextender to make molecular chain is expanded, molecular weight increases small molecule alcohol or amine, chainextender is preferably ethylene glycol, Diethylene Glycol, propylene glycol, 1, one or more in 4-butyleneglycol or 1,6-hexylene glycol.
In described component A, suds-stabilizing agent is also known as foam stabilizer, play a part emulsification foam material, stable foam and adjustment abscess, suds-stabilizing agent is preferably polysiloxane-olefin oxide segmented copolymer, is more preferably one or more in DC193, DC5125 or DC6070 of aerification chemical product company of U.S. production.
In described component A, whipping agent makes viscoelastic foam material expand, foams, solidifies, and obtain urethane foam, whipping agent is preferably water.
In described component A, catalyzer can Reaction time shorten, enhances productivity, and optionally promotes positive reaction, suppresses side reaction, make the balance that foamable reaction and gel reaction reach required.Catalyzer be preferably aerification chemical product company of the U.S. produce Dabco8154, DabcoBL-17 or Dabco33LV in one or more.
In described component A, oxidation inhibitor mainly prevents the thermal-oxidative degradation of urethane, oxidation inhibitor be preferably Taiwan double bond chemical company produce ChinoxTP-10H, ChinoxTP-22, ChinoxTP-25 or ChinoxTP-35 in one or more.
In described component A, photostabilizer mainly prevents from or alleviates urethane, under chronic sun exposure, xanthochromia occurs, photostabilizer be preferably Taiwan double bond chemical company produce ChisorbB2652, ChisorbB2689 or ChisorbB2690 in one or more.
In described component A, solid filler mainly plays a part to reduce production of articles cost and improve to strengthen urethane intensity, and solid filler is preferably the activated Calcium carbonate of median size≤37 micron, whiteness >=90 degree.
In described B component polyether glycol not only raw material be easy to get, with low cost, and the urethane foam performance made is good, be the maximum polyol starting material of urethane foam industry consumption.Polyether glycol be preferably Shandong blue star Dong great chemical company produce EP-3033, EP-240 or ED-28 in one or more.
In described B component, isocyanic ester is the important foundation raw material of synthesis of polyurethane, and raw material sources are extensive, and have good economy, the physical property of product is excellent.Storage stabilizing agent can stop the side reaction of isocyanic ester, can improve the stability in storage of product.Isocyanic ester be preferably BASF Aktiengesellschaft produce LupranateM, LupranateLP30, LupranateMM103C or LupranateM20S in one or more; Storage stabilizing agent is phosphoric acid or Benzoyl chloride.
The preparation method of described polyurethane sport knee-pad composition, comprises the following steps:
(1) component A is prepared: first load weighted special polyether polyvalent alcohol, polyether polyol with high activity, polymer polyatomic alcohol are dropped in reactor and stirred, then the chainextender of accurate measurement, catalyzer, whipping agent, suds-stabilizing agent, photostabilizer, oxidation inhibitor, solid filler is added, under normal temperature after physical agitation 3-4 hour, obtained component A is for subsequent use;
(2) B component is prepared: stir dropping in reactor under load weighted polyether glycol normal temperature, after rising to 80 DEG C-100 DEG C, dewater degassed, then be cooled to 10 ~ 40 DEG C and add the storage stabilizing agent measured, and drop into isocyanic ester, be warming up to 80-85 DEG C of reaction 2-3 hour, after being cooled to 10 ~ 40 DEG C, obtained B component is for subsequent use;
(3) under room temperature, A, B component material are carried out mechanical or manual being mixed to evenly and inject aluminum elbow protector for sports mould, obtain polyurethane sport knee-pad composition through the normal temperature slaking demoulding in 2-10 minute.
In step (2), be evacuated to vacuum tightness≤0.098MPa, dewater degassed 2-3 hour, moisture content≤0.05%.
The present invention has following beneficial effect:
(1) A, B component store in liquid state at normal temperatures, not only save energy but also reduce loaded down with trivial details operation;
(2) adopt full water foamed in formulating of recipe, its ozone layer destroying effect ODP value is zero, asepsis environment-protecting, is a kind of environmental friendliness shaped material;
(3) special polyether polyvalent alcohol and polyether polyol with high activity are successfully applied in polyurethane sport knee-pad composition, prepared polyurethane sport knee-pad goods have excellent antidetonation resiliency and motion comfortableness, thus provide safeguard for the security avoiding joint at the volley to sustain damage, compared with traditional protection tool, substantially increase protection effect;
(4) polyurethane product obtained, except having excellent antidetonation resiliency and motion comfortableness, also has the excellent property such as low-temperature flexibility, sound insulation, sealing in addition.
(5) preparation method of polyurethane sport knee-pad composition of the present invention, is simple and easy to implement, is beneficial to suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated, but it does not limit enforcement of the present invention.
Except special polyether polyvalent alcohol and polyether polyol with high activity, other raw materials used are commercially available prod.
Embodiment 1:
(1) component A material is prepared:
Weigh respectively: (hydroxyl value is 270mgKOH/g to special polyether polyvalent alcohol, functionality is 2.9, with the mixture of propylene glycol and glycerol for initiator) 50Kg, (proportion of primary OH groups is 70% to polyether polyol with high activity, number-average molecular weight is 4000, take glycerol as initiator) 30Kg, polymer polyatomic alcohol POP93/28 is 20Kg, chainextender Diethylene Glycol 1.2Kg, suds-stabilizing agent DC5125 is 1.2Kg, water 3.0Kg, catalyzer Dabco8154 is 1.3Kg, oxidation inhibitor ChinoxTP-22 is 4.1Kg, photostabilizer ChisorbB2652 is 1.4Kg, superfine activated calcium carbonate is 2.0Kg.Load weighted special polyether polyvalent alcohol, polyether polyol with high activity, polymer polyatomic alcohol material are dropped in reactor and stir, then chainextender, catalyzer, foam foaming agent, suds-stabilizing agent, photostabilizer, oxidation inhibitor, the solid filler of accurate measurement is dropped into respectively, physical agitation 3.0 hours at normal temperatures, blowing barrelling warehouse-in from reactor.
(2) B component material is prepared:
Reactor is added by under polyether glycol EP-303320Kg normal temperature, rise to 80 DEG C of stirrings, vacuumize (vacuum tightness≤0.098MPa) and dewater degassed (moisture content 0.05%) 2.0 hours, be cooled to 10 DEG C and add 0.001Kg storage stabilizing agent phosphoric acid, drop into the LupranateM measured is 80Kg simultaneously, 80 DEG C are reacted 2.0 hours, are cooled to 40 DEG C, and barrelling is put in storage.
(3), when using, under room temperature, A, B component material are carried out mechanically mixing to even rear injection aluminum elbow protector for sports mould by the weight proportion of A: B=100: 30, can goods be processed into through the normal temperature slaking demoulding in 3 minutes.
Embodiment 2:
(1) component A material is prepared:
Weigh respectively: (hydroxyl value is 320mgKOH/g to special polyether polyvalent alcohol, functionality is 3.1, with the mixture of propylene glycol and glycol ether for initiator) 65Kg, (proportion of primary OH groups is 70% to polyether polyol with high activity, number-average molecular weight is 8000, with the mixture of glycerol and trolamine for initiator) 20Kg, polymer polyatomic alcohol POP36/28 is 20Kg, chainextender 1, 4-butyleneglycol 0.6Kg, suds-stabilizing agent DC193 is 0.1Kg, water 2.5Kg, catalyzer Dabco33LV is 2.5Kg, oxidation inhibitor ChinoxTP-10H is 1.6Kg, photostabilizer is the mixture of 1.1KgChisorbB2690 and 1.1KgChisorbB2652, superfine activated calcium carbonate is 4.0Kg.Load weighted special polyether polyvalent alcohol, polyether polyol with high activity, polymer polyatomic alcohol material are dropped in reactor and stir, then chainextender, catalyzer, foam foaming agent, suds-stabilizing agent, photostabilizer, oxidation inhibitor, the solid filler of accurate measurement is dropped into respectively, physical agitation 3.5 hours at normal temperatures, blowing barrelling warehouse-in from reactor.
(2) B component material is prepared:
Reactor is added by under polyether glycol EP-24040Kg normal temperature, rise to 85 DEG C of stirrings, vacuumize (vacuum tightness≤0.098MPa) and dewater degassed (moisture content 0.05%) 2.5 hours, be cooled to 20 DEG C and add 0.001Kg storage stabilizing agent phosphoric acid, drop into the LupranateLP30 measured is 60Kg simultaneously, 82 DEG C are reacted 2.5 hours, are cooled to 30 DEG C, and barrelling is put in storage.
(3), when using, under room temperature, A, B component material are carried out mechanically mixing to even rear injection aluminum elbow protector for sports mould by the weight proportion of A: B=100: 45, can goods be processed into through the normal temperature slaking demoulding in 5 minutes.
Embodiment 3:
(1) component A material is prepared:
Weigh respectively: (hydroxyl value is 300mgKOH/g to special polyether polyvalent alcohol, functionality is 3.0, with propylene glycol, the mixture of glycerol and TriMethylolPropane(TMP) is initiator) 80Kg, (proportion of primary OH groups is 75% to polyether polyol with high activity, number-average molecular weight is 5000, take TriMethylolPropane(TMP) as initiator) 10Kg, polymer polyatomic alcohol HPOP40 is 8Kg, chainextender is 0.2Kg1, 6-hexylene glycol, the mixture of 0.5Kg ethylene glycol and 0.5Kg propylene glycol, suds-stabilizing agent DC6070 is 0.2Kg, water 4.5Kg, catalyzer is the mixture of 1.5KgDabco33LV and 1KgDabcoBL-17, oxidation inhibitor ChinoxTP-35 is 1.6Kg, photostabilizer ChisorbB2689 is 2.2Kg, superfine activated calcium carbonate is 5.0Kg.Load weighted special polyether polyvalent alcohol, polyether polyol with high activity, polymer polyatomic alcohol material are dropped in reactor and stir, then chainextender, catalyzer, foam foaming agent, suds-stabilizing agent, photostabilizer, oxidation inhibitor, the solid filler of accurate measurement is dropped into respectively, physical agitation 4.0 hours at normal temperatures, blowing barrelling warehouse-in from reactor.
(2) B component material is prepared:
Reactor is added by under polyether glycol ED-2860Kg normal temperature, rise to 90 DEG C of stirrings, vacuumize (vacuum tightness≤0.098MPa) and dewater degassed (moisture content 0.05%) 3.0 hours, be cooled to 30 DEG C and add 0.001Kg storage stabilizing agent phosphoric acid, drop into the LupranateMM103C measured is 40Kg simultaneously, 85 DEG C are reacted 3.0 hours, are cooled to 20 DEG C, and barrelling is put in storage.
(3), when using, under room temperature, A, B component material are carried out mechanically mixing to even rear injection aluminum elbow protector for sports mould by the weight proportion of A: B=100: 60, can goods be processed into through the normal temperature slaking demoulding in 8 minutes.
Embodiment 4:
(1) component A material is prepared:
Weigh respectively: (hydroxyl value is 290mgKOH/g to special polyether polyvalent alcohol, functionality is 3.0, with the mixture of glycol ether and TriMethylolPropane(TMP) for initiator) 85Kg, (proportion of primary OH groups is 72% to polyether polyol with high activity, number-average molecular weight is 6000, with glycerol, the mixture of trolamine and TriMethylolPropane(TMP) is initiator) 10Kg, polymer polyatomic alcohol is the mixture of 4KgHPOP40 and 4KgPOP93/28, chainextender propylene glycol 1.5Kg, suds-stabilizing agent DC6070 is 0.2Kg, water 3.2Kg, catalyzer DabcoBL-17 is 2.2Kg, oxidation inhibitor is the mixture of 0.6KgChinoxTP-10H and 1KgChinoxTP-25, photostabilizer ChisorbB2690 is 2.2Kg, superfine activated calcium carbonate is 2.0Kg.Load weighted special polyether polyvalent alcohol, polyether polyol with high activity, polymer polyatomic alcohol material are dropped in reactor and stir, then chainextender, catalyzer, foam foaming agent, suds-stabilizing agent, photostabilizer, oxidation inhibitor, the solid filler of accurate measurement is dropped into respectively, physical agitation 3.5 hours at normal temperatures, blowing barrelling warehouse-in from reactor.
(2) B component material is prepared:
Reactor is added by under the polyether polyol mixtures normal temperature of 10KgEP-3033 and 25KgEP-240, rise to 100 DEG C of stirrings, vacuumize (vacuum tightness≤0.098MPa) and dewater degassed (moisture content 0.05%) 2.5 hours, be cooled to 40 DEG C and add 0.001Kg storage stabilizing agent Benzoyl chloride, drop into the LupranateM20S measured is 65Kg simultaneously, 85 DEG C are reacted 2.5 hours, are cooled to 10 DEG C, and barrelling is put in storage.
(3), when using, under room temperature, A, B component material are carried out mechanically mixing to even rear injection aluminum elbow protector for sports mould by the weight proportion of A: B=100: 55, can goods be processed into through the normal temperature slaking demoulding in 8 minutes.
Comparative example 1:
(1) component A material is prepared:
Weigh respectively: (proportion of primary OH groups is 70% to polyether polyol with high activity, number-average molecular weight is 4000, taking glycerol as initiator) 95Kg, polymer polyatomic alcohol HPOP40 be 8Kg, chainextender propylene glycol 1.3Kg, suds-stabilizing agent DC6070 is 0.1Kg, water 3.5Kg, catalyzer Dabco33LV are 2.0Kg, and oxidation inhibitor ChinoxTP-10H is 1.3Kg, photostabilizer ChisorbB2690 is 2.0Kg, and superfine activated calcium carbonate is 1.8Kg.Load weighted special polyether polyvalent alcohol, polyether polyol with high activity, polymer polyatomic alcohol material are dropped in reactor and stir, then chainextender, catalyzer, foam foaming agent, suds-stabilizing agent, photostabilizer, oxidation inhibitor, the solid filler of accurate measurement is dropped into respectively, physical agitation 3.5 hours at normal temperatures, blowing barrelling warehouse-in from reactor.
(2) B component material is prepared:
Be add reactor under 35Kg normal temperature by polyether glycol EP-3033, stir at rising to 100 DEG C, vacuumize (vacuum tightness≤0.098MPa) and dewater degassed (moisture content 0.05%) 2.5 hours, be cooled to the storage stabilizing agent phosphoric acid (accounting for 0.001% of B component gross weight) that 40 DEG C add accurate measurement, drop into the LupranateM measured is 65Kg simultaneously, 85 DEG C are reacted 2.5 hours, are cooled to 10 DEG C, and barrelling is put in storage.
(3), when using, under room temperature, A, B component material are carried out mechanically mixing to even rear injection aluminum elbow protector for sports mould by the weight proportion of A: B=100: 55, can goods be processed into through the normal temperature slaking demoulding in 8 minutes.
The performance test that table 1 embodiment 1-4 and comparative example 1 obtain product is as follows:
Note: Mechanics Performance Testing adopts GB/T528-1998 to test.
Claims (7)
1. a polyurethane sport knee-pad composition, is characterized in that: be made up of component A and B component, and the weight ratio of A, B component is 100: 30-60, wherein:
(1) component A is made up of the component of following parts by weight:
Polyether glycol A:50-85 part,
Polyether glycol B:5-30 part,
Polymer polyatomic alcohol: 5-30 part,
Chainextender: 0.1-1.5 part,
Suds-stabilizing agent: 0.1-1.5 part,
Whipping agent: 2.5-4.5 part,
Catalyzer: 0.1-2.5 part,
Oxidation inhibitor: 0.1-5.0 part,
Photostabilizer: 0.1-5.0 part,
Solid filler: 0.1-5.0 part;
The hydroxyl value of described polyether glycol A is 270 ~ 320mgKOH/g, functionality is 2.9 ~ 3.1, using two or more in propylene glycol, glycerol, glycol ether or TriMethylolPropane(TMP) as mixing initiator, by 1,2-propylene oxide ring-opening polymerization or obtain, mass content≤20% of its ethylene oxide with oxyethane copolymerization;
Proportion of primary OH groups >=70% of described polyether glycol B, number-average molecular weight is 4000 ~ 8000, is with one or more in glycerol, trolamine or TriMethylolPropane(TMP) for initiator, the polyoxytrimethylene trivalent alcohol obtained by ethylene oxide-capped;
Described polymer polyatomic alcohol is one or more in POP36/28, POP93/28 or HPOP40;
(2) B component is made up of the component of following parts by weight:
Polyether glycol C:20-60 part,
Isocyanic ester: 40-80 part,
Storage stabilizing agent: account for 0.001% of B component gross weight;
Described polyether glycol be Shandong blue star Dong great chemical company produce EP-3033, EP-240 or ED-28 in one or more.
2. polyurethane sport knee-pad composition according to claim 1, is characterized in that: chainextender is one or more in ethylene glycol, Diethylene Glycol, propylene glycol, BDO or 1,6-hexylene glycol; Suds-stabilizing agent is polysiloxane-olefin oxide segmented copolymer; Whipping agent is water.
3. polyurethane sport knee-pad composition according to claim 1, is characterized in that: catalyzer is one or more in Dabco8154, DabcoBL-17 or Dabco33LV; Oxidation inhibitor be Taiwan double bond chemical company produce ChinoxTP-10H, ChinoxTP-22, ChinoxTP-25 or ChinoxTP-35 in one or more; Photostabilizer be Taiwan double bond chemical company produce ChisorbB2652, ChisorbB2689 or ChisorbB2690 in one or more.
4. polyurethane sport knee-pad composition according to claim 1, is characterized in that: solid filler is the activated Calcium carbonate of median size≤37 micron, whiteness >=90 degree.
5. polyurethane sport knee-pad composition according to claim 1, is characterized in that: isocyanic ester be BASF Aktiengesellschaft produce LupranateM, LupranateLP30, LupranateMM103C or LupranateM20S in one or more; Storage stabilizing agent is phosphoric acid or Benzoyl chloride.
6. a preparation method for the arbitrary described polyurethane sport knee-pad composition of claim 1-5, is characterized in that comprising the following steps:
(1) component A is prepared: first load weighted polyether glycol A, polyether glycol B, polymer polyatomic alcohol are stirred, then the chainextender of accurate measurement, catalyzer, whipping agent, suds-stabilizing agent, photostabilizer, oxidation inhibitor, solid filler is added, stir 3-4 hour under normal temperature, obtained component A is for subsequent use;
(2) B component is prepared: stir under load weighted polyether glycol C normal temperature, after rising to 80 DEG C-100 DEG C, dewater degassed, then 10 ~ 40 DEG C are cooled to, add the storage stabilizing agent measured, and drop into isocyanic ester, be warming up to 80-85 DEG C of reaction 2-3 hour, be cooled to 10 ~ 40 DEG C, obtained B component is for subsequent use;
(3) A, B component material are mixed under room temperature, then inject aluminum elbow protector for sports mould, the slaking demoulding obtains polyurethane sport knee-pad composition.
7. the preparation method of polyurethane sport knee-pad composition according to claim 6, it is characterized in that: in step (2), be evacuated to vacuum tightness≤0.098MPa, dewater degassed 2-3 hour, moisture content≤0.05%.
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| CN107987240B (en) * | 2017-12-14 | 2021-08-06 | 山东一诺威体育产业有限公司 | Polyurethane composition for protective clothing and preparation method thereof |
| CN109679058A (en) * | 2018-11-28 | 2019-04-26 | 耿佃勇 | Polyurethane protector and preparation method thereof |
| CN109851743A (en) * | 2018-12-18 | 2019-06-07 | 山东一诺威聚氨酯股份有限公司 | Water absorption resistance polyurethane sport knee-pad combination material and preparation method thereof |
| CN111605116B (en) * | 2020-06-11 | 2022-06-28 | 泉州耐优防护用品有限公司 | Production process of knee pad with honeycomb-shaped pouring foaming soft inner pad |
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