CN116655887A - Flame-retardant polyurethane sealing foam and preparation method thereof - Google Patents
Flame-retardant polyurethane sealing foam and preparation method thereof Download PDFInfo
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- CN116655887A CN116655887A CN202310371514.7A CN202310371514A CN116655887A CN 116655887 A CN116655887 A CN 116655887A CN 202310371514 A CN202310371514 A CN 202310371514A CN 116655887 A CN116655887 A CN 116655887A
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
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- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
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- C08G18/40—High-molecular-weight compounds
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- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5003—Polyethers having heteroatoms other than oxygen having halogens
- C08G18/5006—Polyethers having heteroatoms other than oxygen having halogens having chlorine and/or bromine atoms
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
- C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C08G2110/0083—Foam properties prepared using water as the sole blowing agent
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Abstract
The invention discloses flame-retardant polyurethane sealing foam and a preparation method thereof. Comprises a two-component system of a polyol composition (A component) and isocyanate (B component), wherein the weight ratio of A/B is 100/54-66, and the two-component system is directly cast on the sealing of a fitting after fully mixing by a glue spreaderWhere a strip-like sealing foam is formed. The reactant has better anti-flowing property, and the foam can have both sealing property and flame retardance. Foam density of 300-350kg/m 3 The foam has permanent deformation less than 10% and flame retardance up to V-0. The sealing foam is suitable for sealing household electrical appliance plastic parts, lighting fixtures, electronic product cabinets, power distribution cabinets, power battery boxes and the like, and is particularly suitable for accessories with flame retardant performance requirements.
Description
Technical Field
The invention relates to the field of polyurethane, in particular to a process technology for polyurethane on-site pouring foaming reaction molding.
Background
In the fields of construction, household appliances, automobiles, electromechanics and the like, the sealing material is an indispensable chemical product, and can play roles of seepage prevention, leakage prevention, vibration prevention and sealing after seam sealing and non-structural bonding assembly. In these application scenarios, sag resistance and flow resistance of the sealing material polymer before reaction curing are one of the key properties. In a continuous production line, in order to adjust the reaction curing speed and the raw material proportion, A, B dual-component sealing materials are often used, A, B materials are mixed and poured onto a sealing element at a high speed through a glue spreader on site, the requirements on sagging resistance and anti-flowing performance are higher, and otherwise, the appearance shape required by the sealing material cannot be obtained. The patent CN114989390a relates to the process technology in this aspect, and uses the cohesive force and the reactivity between the molecules of the raw material to effectively solve the application deficiency of fumed silica.
In some application scenarios, the appearance and basic physical properties of the sealing material are only basic functions capable of playing a role in sealing, and besides, other functional requirements, such as flame retardance, are common main requirements.
The common technique for preparing the flame retardant material is to add flame retardant, wherein the liquid flame retardant comprises tri (chloropropyl) phosphate, tri (2-chloroethyl) phosphate, triethyl phosphate, triphenyl phosphate and the like, and the inorganic solid flame retardant comprises aluminum hydroxide, melamine, ammonium polyphosphate, expandable graphite and the like. Flame-retardant polyol is also used in the preparation of the polyurethane flame-retardant material, and phosphorus and halogen elements are introduced into the molecular chain of the polyol, so that the flame-retardant effect is achieved, and the negative influence caused by migration of the liquid flame retardant can be avoided. The flame retardant polyol is generally applied to polyurethane rigid foam (or semi-rigid foam), and is suitable for heat insulation places with flame retardant requirements by adopting a conventional foaming technology. Chinese patents CN114853998A, CN115141345, CN115304762 relate to this application technology. In addition, CN106279623a solves the problem of using TDI kettle residues, which are used for preparing polyurethane rigid foam, and the use of chain extender and inorganic filler is mentioned in the specification, in order to improve the compression strength of foam. CN114763433a solves the dimensional stability problem of low density polyurethane microcellular foam, and fumed silica is used for the purpose of improving the cell opening property of the foam.
The polyurethane A, B material is formed by in-situ casting foaming, and is characterized by larger viscosity and small casting quantity of raw materials. In order to achieve the desired flame retardant effect, if a liquid flame retardant is used alone, more fumed silica needs to be added, which results in a foam having poor resilience and seriously affects the sealing effect of the foam. The solid flame retardant also has the use problems of blocking equipment pipelines, and has stiff foam and poor application effect.
Disclosure of Invention
The invention aims to provide flame-retardant polyurethane sealing foam and a preparation method thereof, which aim to solve the problems of flow resistance and foam flame retardance of A, B material in-situ pouring reaction. According to the invention, the flame-retardant polyether polyol and the high-reactivity cross-linking agent component are introduced into the component A of the combined polyether, and the foam can be compatible with manufacturability, sealability and flame retardance.
In order to achieve the above object, the present invention adopts the following technical scheme:
the flame-retardant polyurethane sealing foam comprises the following A, B raw materials:
and (3) a component A: a polyol composition comprising the following components:
polyols, including polyether polyols and flame retardant polyether polyols;
amine organic matters;
a chain extender;
fumed silica;
water, surfactant and catalyst;
and (3) isocyanate of the component B.
In the flame-retardant polyurethane sealing foam, the weight ratio of the component A to the component B is 100:54-66; preferably, the weight ratio of the A component to the B component is 100:57-63.
As a preferred embodiment, the content of each component is, based on 100% by weight of the polyol composition: 92-95% of polyalcohol, 0.5-1.5% of amine organic matters, 1-3% of chain extender, 1.9-2.1% of fumed silica, 0.45-0.55% of water, 0.5-0.8% of surfactant and 0.5-0.7% of catalyst.
As another preferred embodiment, the polyol composition further comprises a black paste, preferably in an amount of 0.3 to 0.5%.
In the component A of the present invention, the initiator of the polyether polyol comprises one or more of glycerin, trimethylolpropane and pentaerythritol, and is obtained by polymerization with propylene oxide and/or ethylene oxide, preferably having a hydroxyl value of 20 to 50mgKOH/g.
The initiator of the flame-retardant polyether polyol is tetrabromobisphenol A, and is polymerized with propylene oxide, and the hydroxyl value is preferably 100-140mgKOH/g.
Preferably, the polyol comprises the following composition (wherein weight ratio refers to weight ratio in polyol):
polyether polyol 1: starting with glycerol and capping with ethylene oxide, and having a hydroxyl value of 32-36mgKOH/g; and/or polyether polyol 2, glycerol-initiated, ethylene oxide-capped, hydroxyl number of 26-30mgKOH/g; 25-60wt%;
polyether polyol 3: starting pentaerythritol, end capping ethylene oxide, and hydroxyl value of 30-34mgKOH/g; 0-10wt% of a weight ratio;
flame retardant polyether polyol 4: tetrabromobisphenol A and propylene oxide are polymerized to obtain the product, the hydroxyl value is 100-140mgKOH/g, and the weight ratio is 35-55wt%.
In the component A of the invention, the amine organic matters comprise, but are not limited to, at least one of ethylenediamine, diethyltoluenediamine, dimethylthiotoluenediamine, 4' -di-sec-butylaminodiphenyl methane, 4' -di-diaminodiphenyl methane and 3, 3' -dichloro-4, 4' -diaminodiphenyl methane, preferably diethyltoluenediamine and 4, 4' -di-sec-butylaminodiphenyl methane. The amine organic matters have high reactivity, can react with isocyanate quickly, improve the viscosity of the reactants, and can limit the flow of the cast-in-place reactants.
In the component A of the present invention, the chain extender includes, but is not limited to, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, hexylene glycol, preferably ethylene glycol and/or butylene glycol.
In the component A, the fumed silica is nano-scale white powder generated by high-temperature hydrolysis of silicon halide in oxyhydrogen flame, and the specific surface area of aggregate is more than 200m 2 /g。
In the component A of the invention, the surfactant is ethylene oxide and propylene oxide copolyether modified polysiloxane, which plays roles of emulsification, nucleation and foam stabilization, and commercial products are B8715, DC6070 and the like.
In the component A of the invention, the catalyst comprises one or more of triethylene diamine, dimethylaminoethyl ether, dimorpholine diethyl ether, N-dimethylcyclohexylamine, N-ethylmorpholine, N-methyldicyclohexylamine, pentamethyldiethylenetriamine, triethylamine, dimethylethanolamine and the like, and preferably one or two of triethylene diamine and dimethylaminoethyl ether.
The component B of the invention comprises urethane modified diphenylmethane diisocyanate prepolymer, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate and liquid flame retardant.
The NCO content of the component B is 15.5-16.5%, and the viscosity is 150-200 mPa.S.
Further, the preparation method of the component B disclosed by the invention comprises the following steps: the polyether polyol is reacted with diphenylmethane diisocyanate, followed by the addition of polymethylene polyphenyl isocyanate and a liquid flame retardant.
In the preparation method of the component B, the polyether polyol comprises commercial products such as WANOL F3128, WANOL F3135, 10LD76E, 10LD83E, EP-330N, EP-3600 and the like, has the functionality of 3 and the molecular weight of more than 4800, and has stable and controllable reaction with diphenylmethane diisocyanate, and generally has the NCO content of 18-20 percent, is easy to prepare foam and has better elasticity.
In the preparation method of the component B, the diphenylmethane diisocyanate can use the chemical MDI-100 of Van der Waals.
Polymethylene polyphenyl polyisocyanates include PM-200, LUPRANATE M20S, DESMODUR V20, and the like, also known as polymeric MDI, with the average functionality of the B component adjusted to 2.2-2.4 by the addition of polymeric MDI.
In the component B of the present invention, the liquid flame retardant includes, but is not limited to, tris (chloropropyl) phosphate, tris (2-chloroethyl) phosphate, triethyl phosphate and triphenyl phosphate, preferably tris (chloropropyl) phosphate and tris (2-chloroethyl) phosphate.
In the component B, the polymethylene polyphenyl polyisocyanate is added to improve the low-temperature storage performance of the component B and adjust the functionality of the component B, and the liquid flame retardant is added to further improve the low-temperature storage performance of the component B and endow the foam with flame retardant property.
In a second aspect of the present invention, there is provided a method for preparing a flame retardant polyurethane sealing foam, comprising the steps of: and mixing the component A and the component B by a glue spreader at 20-25 ℃ and then pouring.
It is further explained and illustrated that the flame retardant polyurethane sealing foam of the invention achieves unexpected effects, has excellent anti-flowing property and better flame retardant property. It is possible that the N atom of the amine compound forms a hydrogen bond with the hydroxyl groups on the surface of the fumed silica with stronger binding force, and the flame-retardant polyether polyol has reactive functional groups, unlike the non-reactive flame retardant, all of which cause the foam to have both an ideal shape and better flame retardance. Although a liquid flame retardant is also used in the present invention, this is solely for cost reasons.
Foam density of 300-350kg/m 3 The foam has permanent deformation less than 10% and flame retardance up to V-0.
The scheme of the invention has the advantages of one-step molding, high efficiency and good consistency. By changing the diameter of the hole of the pouring head, the requirements of different sealing strip sizes can be met.
The invention has the beneficial effects that: the production efficiency is high, the appearance of the foam strip is smooth, the connection is good, the sealing effect is good, and the sealing device is suitable for sealing fittings with regular shapes and irregular shapes, and is more suitable for sealing fittings with flame retardant requirements.
The foam product of the invention is foamed in situ, generally has a strip-shaped appearance, is used for sealing household electrical appliance plastic parts, lighting fixtures, electronic product cabinets, power distribution cabinets, power battery boxes and the like, and is particularly suitable for accessories with flame retardant performance requirements.
Detailed Description
The invention will be further illustrated by the following examples, but the invention is not limited to these examples, test methods, and raw materials used as follows.
The viscosity test method comprises the following steps: according to GB/T12008.7-2010
NCO test standard: according to GB/T12009.4-2016
Permanent set test: according to GB/T1683-2018
Flame retardancy test: UL94
Diethyl toluene diamine;
catalyst 1: bis-dimethylaminoethyl ether;
catalyst 2: a DPG solution of 33% triethylenediamine;
polyether polyol 1: starting with glycerol and end capping with ethylene oxide, and having a hydroxyl value of 26-30mgKOH/g;
polyether polyol 2: starting with glycerol and capping with ethylene oxide, and having a hydroxyl value of 32-36mgKOH/g;
polyether polyol 3: starting pentaerythritol, end capping ethylene oxide, and hydroxyl value of 30-34mgKOH/g;
flame-retardant polyether polyol 4, polymerized by tetrabromobisphenol A and propylene oxide, and with a hydroxyl value of 100-140mgKOH/g;
fumed silica: nanoscale white powder produced by hydrolysis of silicon halide in oxyhydrogen flame with specific surface area of aggregate of 200-300m 2 /g。
Diphenylmethane diisocyanate: such as MDI-100 of the Wanhua chemistry.
Polymeric MDI: mixtures of diphenylmethane diisocyanate and polymethylene polyphenyl isocyanates, such as PM-200 of Wanhua chemistry.
Examples
Isocyanate B1: NCO content 15.7%, viscosity 193 mPa.S (25 ℃). 16.9 kg of polyether polyol 1 is added into a reaction kettle, the temperature of the mixture is kept at 60 ℃, 23.4 kg of diphenylmethane diisocyanate is added, and the mixture is kept at 80 ℃ for reaction for 3 hours. Then 26.6 kg of polymeric MDI and 33.1 kg of tris (chloropropyl) phosphate were added.
Isocyanate B2: NCO content 16.3% and viscosity 158 mPa.s (25 ℃). 14.9 kg of polyether polyol 2 is added into a reaction kettle, the temperature of the mixture is kept at 60 ℃, 23.9 kg of diphenylmethane diisocyanate is added, and the mixture is kept at 80 ℃ for reaction for 3 hours. Then 27.8 kg of polymeric MDI and 33.4 kg of tris (2-chloroethyl) phosphate were added.
According to the weight proportion of the raw materials in the table 1 and the table 2 (wherein, the effective content of each component is calculated), firstly, the polyol is added into a charging basket of a dispersing machine, then the aerosil is added, the stirring is carried out at a low speed (50-100 rpm) until the aerosil is wetted, and then the stirring is carried out at a high speed (800-1000 rpm) until the aerosil is dispersed into the polyol raw material. Then adding the rest other components, stirring and mixing for 30 minutes to obtain the component A of the polyol composition.
The component A and the component B of the polyol composition form a two-component system, and the component A, B is directly poured at the sealing part of the accessory after being fully mixed by a glue spreader and is molded at one step.
Table 1 example conditions and product properties
Table 2 comparative example conditions and product Properties
The foam strip in the embodiment has better elasticity and can well achieve both flame retardance and sealing performance. Comparative example 1 is free of amine organics and foam shape is not consistent. In comparative examples 2-3, no flame retardant polyether polyol was used, and a liquid flame retardant was used, and more fumed silica was added to maintain the basic foam shape and flame retardance, but the foam was large in permanent deformation and poor in elasticity, and could not be used for sealing.
The examples are provided for clarity of illustration and are not intended to be limiting. It is within the scope of the present invention that modifications in the proportions of the raw materials, or substitutions of the same type of raw materials, may be made by those skilled in the art on the basis of this description, and that variations derived therefrom remain within the scope of the present invention.
Claims (10)
1. The flame-retardant polyurethane sealing foam comprises the following A, B raw materials:
and (3) a component A: a polyol composition comprising the following components:
polyols, including polyether polyols and flame retardant polyether polyols;
amine organic matters;
a chain extender;
fumed silica;
water, surfactant and catalyst;
and (3) isocyanate of the component B.
2. The flame retardant polyurethane sealing foam of claim 1, wherein the weight ratio of the a component to the B component is 100:54-66; preferably, the weight ratio of the A component to the B component is 100:57-63.
3. The flame retardant polyurethane sealing foam according to claim 1 or 2, wherein the content of each component is, based on 100% by weight of the polyol composition: 92-95% of polyalcohol, 0.5-1.5% of amine organic matters, 1-3% of chain extender, 1.9-2.1% of fumed silica, 0.45-0.55% of water, 0.5-0.8% of surfactant and 0.5-0.7% of catalyst.
4. A flame retardant polyurethane sealing foam according to any one of claims 1 to 3, wherein in component a, the initiator of said polyether polyol comprises one or more of glycerol, trimethylolpropane and pentaerythritol, obtained by polymerisation with propylene oxide and/or ethylene oxide, preferably having a hydroxyl value of 20 to 50mg koh/g; the initiator of the flame-retardant polyether polyol is tetrabromobisphenol A, and is polymerized with propylene oxide, and the hydroxyl value is preferably 100-140mgKOH/g.
5. The flame retardant polyurethane sealing foam of any one of claims 1-4, wherein the polyol comprises the following composition:
polyether polyol 1: starting with glycerol and capping with ethylene oxide, and having a hydroxyl value of 32-36mgKOH/g; and/or polyether polyol 2, glycerol-initiated, ethylene oxide-capped, hydroxyl number of 26-30mgKOH/g; 25-60wt%;
polyether polyol 3: starting pentaerythritol, end capping ethylene oxide, and hydroxyl value of 30-34mgKOH/g; 0-10wt% of a weight ratio;
flame retardant polyether polyol 4: tetrabromobisphenol A and propylene oxide are polymerized to obtain the product, the hydroxyl value is 100-140mgKOH/g, and the weight ratio is 35-55wt%.
6. The flame retardant polyurethane sealing foam according to any one of claims 1 to 5, wherein said amine-based organic compound comprises at least one of ethylenediamine, diethyltoluenediamine, dimethylthiotoluenediamine, 4' -bis-secondary butylaminodiphenyl methane, 4' -bis-diaminodiphenyl methane and 3, 3' -dichloro-4, 4' -diaminodiphenyl methane, preferably diethyltoluenediamine and 4, 4' -bis-secondary butylaminodiphenyl methane.
7. The flame retardant polyurethane sealing foam according to any one of claims 1-6, wherein the catalyst comprises one or more of triethylenediamine, bis-dimethylaminoethyl ether, dimorpholine diethyl ether, N-dimethylcyclohexylamine, N-ethylmorpholine, N-methyldicyclohexylamine, pentamethyldiethylenetriamine, triethylamine and dimethylethanolamine, preferably one or both of triethylenediamine and bis-dimethylaminoethyl ether.
8. The flame retardant polyurethane sealing foam according to any one of claims 1 to 7, wherein the B component comprises urethane modified diphenylmethane diisocyanate prepolymer, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate and liquid flame retardant.
9. The flame retardant polyurethane sealing foam of claim 8, wherein the NCO content of the urethane modified diphenylmethane diisocyanate prepolymer in the B component is 18 to 20%; the NCO content of the component B is 15.5-16.5%, and the viscosity is 150-200 mPa.S.
10. A method of preparing the flame retardant polyurethane sealing foam of any one of claims 1-9, comprising the steps of: and mixing the component A and the component B by a glue spreader at 20-25 ℃ and then pouring.
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| CN202310371514.7A CN116655887A (en) | 2023-04-10 | 2023-04-10 | Flame-retardant polyurethane sealing foam and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119306910A (en) * | 2024-12-19 | 2025-01-14 | 山东一诺威新材料有限公司 | Low-reaction thermal reinforcement material for mines and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119306910A (en) * | 2024-12-19 | 2025-01-14 | 山东一诺威新材料有限公司 | Low-reaction thermal reinforcement material for mines and preparation method thereof |
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