CN103709395A - Biomass base structure flame retardant polyol and preparation method and application thereof - Google Patents
Biomass base structure flame retardant polyol and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses biomass base structure flame retardant polyol and a preparation method and an application thereof. An intermediate is obtained by utilizing the Mannich reaction of biomass anacardol, diethanolamine, melamine or urea, and formaldehyde, and the biomass base structure flame retardant polyol can be prepared through further alkoxylation with epoxy ethane and epoxy propane, with a hydroxyl value of 200-500mg/gKOH, moisture being less than or equal to 1.0%, and viscosity of 2000-10000mPa.s (25 DEG C), and the biomass base structure flame retardant polyol is applied in polyurethane foam as a polyol component. According to the biomass base structure flame retardant polyol as well as the preparation method and the application, an intermediate process does not need separation, the cost is low, the process is easy, and the prepared polyurethane foam is good in flame retardance, has the advantages that a product does not drip liquid, the shape is kept, the smoke density is low and the like, and can be used in construction, heat preservation and some special fields.
Description
Technical field
The present invention relates to a kind of biomass-based structure flame retarded polyurethane-foam and preparation method thereof, relate generally to the preparation of biomass-based structure flame-proof polyol and the application in polyurethane foam as polyol component, be particularly suitable for preparing the preparation of the flame-retardant polyurethane spray coating heat preservation material of pentamethylene foaming system.
Background technology
Urethane is the superpolymer that contains carbamate groups (NHCOO-) in molecule chain.The difference of raw material, auxiliary agent and processing condition, can synthesize the different product of performance, such as porous plastics, rubber, coating, tackiness agent, spandex fiber etc. when synthetic.Polyurethane foam is the current heat-insulating material of performance the best in the world, because the developed countries such as America and Europe pay much attention to building energy conservation, so in these countries, hard polyurethane foam has been widely used in the roof, body of wall, top ceiling, floor, door and window of buildings etc.But the density of urethane foam is little, specific surface area is large, compares more easily burning with non-foam material, and burning and decomposition produce a large amount of toxic smogs.Meeting fire can burn and decompose, and during burning, hot burst size is large, produces a large amount of toxic smogs, and HUMAN HEALTH and environment are had to very bad impact.Therefore, the flame resistivity of rigid urethane foam, security, can become for the important technology index of lagging material.
The patent of relevant biomass-based flame retarded polyurethane-foam plastics particularly structure flame retarded polyurethane-foam plastics is few, be mainly with biomass-making for polyvalent alcohol, then in formula, add fire retardant to prepare and in flame retarded polyurethane-foam plastics CN1543478A, disclose the method for utilizing xylogen to prepare urethane, the method comprises makes the many alcoholic solutions and the polyisocyanates generation polycondensation that contain lignosulfonic acid or its part neutralized salt with dissolved state, because xylogen composition can not play the effect that macromole polyfunctionality is cross-linked core in urethane, cause the bonding properties of xylogen composition and urethane poor, and the flame retardant properties of the urethane of preparation is general.CN102585143A discloses a kind of biomass-based flame retardant polyurethane foams and preparation method thereof, comprises and utilizes modified lignin to prepare flame retarded polyurethane-foam plastics together with other raw materials, and synthesis technique is more complicated.
The disclosed a kind of biomass-based structure flame retardant type polyvalent alcohol of this patent, viscosity is low, and active high, technique is simple.
Summary of the invention
The technical problem solving: the object of this invention is to provide a kind of biomass-based structure flame retardant type polyvalent alcohol, and utilize biomass cardanol, diethanolamine, trimeric cyanamide or urea, formaldehyde to react and obtain intermediate by Mannich, further carry out with the mixture of oxyethane and propylene oxide the method that alkoxide is prepared biomass-based structure flame retardant type polyvalent alcohol again, and the application in polyurethane foam as polyol component, be particularly suitable for preparing polyurethane coating lagging material, improve and do with it flame retardant properties that raw material is prepared polyurethane foam.
Technical scheme: biomass-based structure flame retardant type polyvalent alcohol, after being mixed by cardanol and formaldehyde, drip diethanolamine, by Mannich, react and obtain cashew nut phenolic group Mannich alkali intermediate, further carrying out alkoxide with oxyethane and propylene oxide again makes, its viscosity is 2000-10000mPas (25 ℃), and hydroxyl value is 200-500mg/g KOH, moisture≤1.0%wt; Wherein the mol ratio of cardanol, diethanolamine and formaldehyde is 1:1:1-1:3:3, oxyethane and propylene oxide for arbitrarily than and total mole number be 1-14 times of cardanol mole number, the reaction conditions of preparing cashew nut phenolic group Mannich alkali intermediate is 60-100 ℃, diethanolamine time for adding is 1-2h, and the reaction times is 2-4h; React the complete water of removing in reaction system, when water-content is less than 1.5%wt, carry out alkoxide reaction, temperature of reaction is 120 ℃～140 ℃, and the reaction times is 2～5 hours.
In described Mannich reaction system, also comprise trimeric cyanamide or urea, the addition of trimeric cyanamide or urea is no more than 30% of cardanol weight.
The preparation method of biomass-based structure flame retardant type polyvalent alcohol, step is by after cardanol and formaldehyde mixing, drips diethanolamine, by Mannich, react and obtain Mannich alkali intermediate, described Mannich reaction conditions is 60-100 ℃, and diethanolamine time for adding is 1-2h, and the reaction times is 2-4h; React the complete water of removing in solution, when moisture content is less than 1.5%, further carries out alkoxide with oxyethane and propylene oxide again and make, temperature of reaction is 120 ℃～140 ℃, and the reaction times is 2～5 hours; Wherein the mol ratio of cardanol, diethanolamine and formaldehyde is 1:1:1-1:3:3, oxyethane and propylene oxide for arbitrarily than and total mole number be 1-14 times of cardanol mole number.In Mannich reaction system, also comprise trimeric cyanamide or urea, the addition of trimeric cyanamide or urea is no more than 30% of cardanol weight.
The mol ratio of described cardanol, diethanolamine and formaldehyde is 1:2:2.
The addition of described trimeric cyanamide or urea is the 15-20% of cardanol weight.
The application of described biomass-based structure flame retardant type polyvalent alcohol in preparing the flame-retardant polyurethane spray coating heat preservation material of pentamethylene foaming system.
The application of described biomass-based structure flame retardant type polyvalent alcohol in preparation polyurethane foam.
The application of described biomass-based structure flame retardant type polyvalent alcohol in preparation polyurethane foam, by mass parts, preparation process is: the biomass-based structure flame retardant type of a. polyvalent alcohol 50-100 part; B. mixture 0.1-0.6 part of amines catalyst or amines catalyst and tin class catalyzer, wherein, amines catalyst is N, N, a kind of or any several mixture in-dimethylcyclohexylamine, triethylenediamine, dimethyl benzylamine, trolamine, α-amino isopropyl alcohol, quaternary amine, tin class catalyzer is di-n-butyltin dilaurate; C. suds-stabilizing agent 0.5-5 part; D. whipping agent 10-30 part, water 0.01-5 part; By above-mentioned component mixing and stirring, then with isocyanic ester mix and blend 20-30s, rotating speed 3000-3500r/min, pours in mould, slaking 48h, during foaming, isocyanic ester and polyvalent alcohol are 1.2～2.5 by the mol ratio of NCO/OH; Described isocyanic ester is tolylene diisocyanate, Xylene Diisocyanate or polymethine polyphenyl polyisocyanate (PAPI).Described biomass-based structure flame retardant type polyvalent alcohol is the application in polyurethane foam in preparation, also comprises the polyester polyol of hydroxyl value 250～450mgKOH/g in mixture, and consumption is no more than 50 parts.
Beneficial effect: 1. in biomass-based structure flame retardant type polyvalent alcohol, contain phenol ring, nitrogen heterocyclic structure, with other polyol phase ratios, heat-resisting, the fire-retardant and mechanical property having had.2. the structure flame retardant type polyvalent alcohol combination material compatibility that the pentamethylene of take is foaming system is good, and stability in storage is high.3. cardanol is renewable resources, and the material of preparation has ecologic effect.4. in structure flame retardant type polyvalent alcohol, contain tertiary amine structure, reactive behavior is high, does not add catalyzer or add less catalyzer to be easy to prepare polyurethane coating lagging material.In subordinate list 1, show, the structure flame retardant type polyvalent alcohol that embodiment 1～6 obtains, in application, show the rigid urethane foam sample being prepared containing structure flame retardant type polyvalent alcohol by the present invention, with other polyol phase ratios, there is catalyst levels few, flame retardant resistance, thermotolerance and good mechanical performance.
Accompanying drawing explanation
Fig. 1 is cashew nut phenolic group Mannich alkali intermediate infrared spectra, as seen from the figure: 33540cm
-1place for-OH and-vibration absorption peak of NH; 2945cm
-1, 2878cm
-1place is the stretching vibration absorption peak of methyl, methylene radical; 1660cm
-1stretching vibration absorption peak for trimeric cyanamide N=C; 1450cm
-1absorption peak for C-N; 1252cm
-1stretching vibration absorption peak for ν C-O in alcohol amine structure; 1027cm
-1the flexural vibration absorption peak of C-O-C.
Fig. 2 is biomass based structures flame retardant type polyvalent alcohol infrared spectra, as seen from the figure: 3352cm
-1place for-OH and-vibration absorption peak of NH; 2925cm
-1, 2854cm
-1place is the stretching vibration absorption peak of methyl, methylene radical; 1620cm
-1stretching vibration absorption peak for cardanol phenyl ring C=C; 1455cm
-1absorption peak for C-N; 1264cm
-1stretching vibration absorption peak for polyether glycol terminal hydroxy group ν C-O; 1077cm
-1the flexural vibration absorption peak of C-O-C.
Embodiment
Following examples further illustrate content of the present invention, but should not be construed as limitation of the present invention.Without departing from the spirit and substance of the case in the present invention, the modification that the inventive method, step or condition are done and replacement, all belong to scope of the present invention.Embodiment 1:
By cardanol 302g, 37%wt formaldehyde solution 162g adds in reactor and mixes, be warmed up to 70 ℃, drip diethanolamine 210g, time for adding is 1h, drip and finish at 90 ℃ of reaction 3h, continue to be warmed up to 110 ℃, decompression dehydration, when moisture content≤1.5%wt, circulation passes into 66g oxyethane and 87g propylene oxide carries out alkoxide reaction, temperature of reaction is controlled at 120-130 ℃, pressure-controlling is at 0.3-0.5MPa, led to after epoxide, constant temperature and pressure reaction 60min, at 120 ℃/10 ㎜ Hg, the 30min that finds time reduces pressure, obtain structure flame retardant type polyvalent alcohol, its hydroxyl value is 386mg/g KOH, 25 ℃ of viscosity are 2100mPas.Then according to the preparation formula of table 1 rigid urethane foam, obtain combining polyvalent alcohol, stir, then mix high-speed stirring 20-30s with isocyanic ester, rotating speed 3000-3500r/min, pours in mould, slaking 48h.
Embodiment 2:
By cardanol 302g, paraformaldehyde 60g, trimeric cyanamide 30g adds in reactor and mixes, be warmed up to 70 ℃, drip diethanolamine 210g, time for adding is 1h, drip and finish at 90 ℃ of reaction 3h, continue to be warmed up to 110 ℃, decompression dehydration, when moisture content≤1.5%wt, circulation passes into 80g oxyethane and 97g propylene oxide carries out alkoxide reaction, temperature of reaction is controlled at 120-130 ℃, pressure-controlling is at 0.3-0.5MPa, led to after epoxide, constant temperature and pressure reaction 60min, at 120 ℃/10 ㎜ Hg, the 30min that finds time reduces pressure, obtain structure flame retardant type polyvalent alcohol.Its hydroxyl value is 406mg/g KOH, and 25 ℃ of viscosity are 5100mPas.Then according to the preparation formula of table 1 rigid urethane foam, obtain combining polyvalent alcohol, stir, then mix high-speed stirring 20-30s with isocyanic ester, rotating speed 3000-3500r/min, pours in mould, slaking 48h.
Embodiment 3:
By cardanol 302g, 37%wt formaldehyde solution 243g, trimeric cyanamide 60g adds in reactor and mixes, be warmed up to 80 ℃, drip diethanolamine 315g, time for adding is 2h, drip and finish at 100 ℃ of reaction 4h, continue to be warmed up to 110 ℃, decompression dehydration, when moisture content≤1.5%wt, circulation passes into 134g oxyethane and 163g propylene oxide carries out alkoxide reaction, temperature of reaction is controlled at 120-130 ℃, pressure-controlling is at 0.3-0.5MPa, led to after epoxide, constant temperature and pressure reaction 60min, at 120 ℃/10 ㎜ Hg, the 30min that finds time reduces pressure, obtain structure flame retardant type polyvalent alcohol.Its hydroxyl value is 460mg/g KOH, and 25 ℃ of viscosity are 8500mPas.Then according to the preparation formula of table 1 rigid urethane foam, obtain combining polyvalent alcohol, stir, then mix high-speed stirring 20-30s with isocyanic ester, rotating speed 3000-3500r/min, pours in mould, slaking 48h.
Embodiment 4:
By cardanol 302g, paraformaldehyde 60g, trimeric cyanamide 90g adds in reactor and mixes, be warmed up to 80 ℃, drip diethanolamine 210g, time for adding is 1h, drip and finish at 90 ℃ of reaction 3h, obtain cashew nut phenolic group Mannich alkali intermediate (Fig. 1), continue to be warmed up to 110 ℃, decompression dehydration, when moisture content≤1.5%wt, pass into 220g oxyethane and carry out alkoxide reaction, temperature of reaction is controlled at 120-130 ℃, pressure-controlling is at 0.3-0.5MPa, led to after epoxide, constant temperature and pressure reaction 60min, at 120 ℃/10 ㎜ Hg, the 30min that finds time reduces pressure, obtain structure flame retardant type polyvalent alcohol (Fig. 2).Its hydroxyl value is 452mg/gKOH, and 25 ℃ of viscosity are 9800mPas.Then according to the preparation formula of table 1 rigid urethane foam, obtain combining polyvalent alcohol, stir, then mix high-speed stirring 20-30s with isocyanic ester, rotating speed 3000-3500r/min, pours in mould, slaking 48h.
Embodiment 5:
By cardanol 302g, 37%wt formaldehyde solution 162g, trimeric cyanamide 45g adds in reactor and mixes, be warmed up to 80 ℃, drip diethanolamine 210g, time for adding is 1h, drip and finish at 90 ℃ of reaction 3h, continue to be warmed up to 110 ℃, decompression dehydration, when moisture content≤1.5%wt, circulation passes into 144g oxyethane and 160g propylene oxide carries out alkoxide reaction, temperature of reaction is controlled at 120-130 ℃, pressure-controlling is at 0.3-0.5MPa, led to after epoxide, constant temperature and pressure reaction 60min, at 120 ℃/10 ㎜ Hg, the 30min that finds time reduces pressure, obtain structure flame retardant type polyvalent alcohol.Its hydroxyl value is 480mg/g KOH, and 25 ℃ of viscosity are 8800mPas.Then according to the preparation formula of table 1 rigid urethane foam, obtain combining polyvalent alcohol, stir, then mix high-speed stirring 20-30s with isocyanic ester, rotating speed 3000-3500r/min, pours in mould, slaking 48h.
Embodiment 6:
Cardanol 302g, 37%wt formaldehyde solution 162g, urea 60g are added in reactor and mixed, be warmed up to 80 ℃, drip diethanolamine 210g, time for adding is 1h, drip and finish at 90 ℃ of reaction 3h, continue to be warmed up to 110 ℃, decompression dehydration, when moisture content≤1.5%wt, pass into 240g propylene oxide and carry out alkoxide reaction, temperature of reaction is controlled at 120-130 ℃, and pressure-controlling, at 0.3-0.5MPa, has been led to after epoxide, constant temperature and pressure reaction 60min, at 120 ℃/10 ㎜ Hg, the 30min that finds time that reduces pressure, obtains structure flame retardant type polyvalent alcohol.Its hydroxyl value is 432mg/g KOH, and 25 ℃ of viscosity are 8400mPas.Then according to the preparation formula of table 1 rigid urethane foam, obtain combining polyvalent alcohol, stir, then mix high-speed stirring 20-30s with isocyanic ester, rotating speed 3000-3500r/min, pours in mould, slaking 48h.
Rigid urethane foam prepare dispensing information:
Catalyzer: be composite catalyst; The mixture of amines catalyst or amines catalyst and tin class catalyzer.Wherein, amines catalyst is selected from: N, N ,-dimethylcyclohexylamine, triethylenediamine, dimethyl benzylamine, trolamine, α-amino isopropyl alcohol, quaternary amine or similar catalyzer, can be one of above-mentioned substance, also can the two or more mixtures with arbitrary proportion.Tin class catalyzer is selected from: di-n-butyltin dilaurate and similarly catalyzer.
Suds-stabilizing agent: silicon-oxygen or silicon-charcoal type tensio-active agent, dolantin Shi Chuan company produces suds-stabilizing agent AK8805, AK8815, AK8812, AK8809 etc.; German Sa company: B8460, B8481, B8474, B8471, B8476, B8481 etc.Suds-stabilizing agent can be one of above-mentioned can be also that two or more arbitrary proportion mixes and uses.
Whipping agent: pentamethylene, weight ratio 100:10～30 when combination polyvalent alcohol mixes with whipping agent.
Isocyanic ester can be selected from: tolylene diisocyanate, Xylene Diisocyanate, polymethine polyphenyl polyisocyanate (PAPI), and preferred PAPI, trade names are: Desmodur N, the 44V20L of Bayer company, 44V10L etc.; The Superace5005 of Huntsman company, 2085 etc.; The PAPI27 of DOW company; The MR200 of BASF AG; The PM2010 of Yantai Wan Hua company etc.During foaming, isocyanic ester and combined polyether (ester) are 1.2～2.5 by the mol ratio of NCO/OH.
Table 2 is the performance measurement result of rigid urethane foam after modification:
The formula (mass parts) of table 1 embodiment 1～6 combination polyvalent alcohol
Table 2 urethane foam product performance (testing method is with reference to national standard)
Mensuration shows: the structure flame retardant type polyvalent alcohol preparing with the present invention replaces common polyvalent alcohol by mass parts 50～100%, obtains flame-retardant hard polyurethane foaming plastic sample, has good mechanical property, thermostability and flame retardant resistance; Oxygen index 22-28%, smoke density grade (SDR) is 62-87; Can in higher envrionment temperature, use, save the energy.
It is raw material that the present invention adopts forestry biomass cardanol, by with diethanolamine, trimeric cyanamide or urea, formaldehyde reaction, obtain intermediate further and then carry out alkoxide with oxyethane and propylene oxide just making structure flame retardant type polyvalent alcohol.The advantages such as this technique pilot process does not need separation, and cost is lower, and technique is simple, and the Polyurethane Rigid Foam Flame Retardance performance of preparation is significantly improved, and goods No drip type while having burning, keeps shape, and smoke density is little.
Claims (10)
1. biomass-based structure flame retardant type polyvalent alcohol, after it is characterized in that being mixed by cardanol and formaldehyde, drip diethanolamine, by Mannich, react and obtain cashew nut phenolic group Mannich alkali intermediate, further carrying out alkoxide with oxyethane and propylene oxide again makes, 25 ℃ of its viscosity are 2000-10000 mPas, and hydroxyl value is 200-500 mg/g KOH, moisture≤1.0%wt; Wherein the mol ratio of cardanol, diethanolamine and formaldehyde is 1:1:1-1:3:3, oxyethane and propylene oxide for arbitrarily than and total mole number be 1-14 times of cardanol mole number, the reaction conditions of preparing cashew nut phenolic group Mannich alkali intermediate is 60-100 ℃, diethanolamine time for adding is 1-2h, and the reaction times is 2-4h; React the complete water of removing in reaction system, when water-content is less than 1.5%wt, carry out alkoxide reaction, temperature of reaction is 120 ℃ ~ 140 ℃, and the reaction times is 2 ~ 5 hours.
2. biomass-based structure flame retardant type polyvalent alcohol according to claim 1, is characterized in that also comprising trimeric cyanamide or urea in Mannich reaction system, and the addition of trimeric cyanamide or urea is no more than 30% of cardanol weight.
3. the preparation method of biomass-based structure flame retardant type polyvalent alcohol, it is characterized in that step is by after cardanol and formaldehyde mixing, drip diethanolamine, by Mannich, react and obtain Mannich alkali intermediate, described Mannich reaction conditions is 60-100 ℃, diethanolamine time for adding is 1-2h, and the reaction times is 2-4h; React the complete water of removing in solution, when moisture content is less than 1.5%, further carries out alkoxide with oxyethane and propylene oxide again and make, temperature of reaction is 120 ℃ ~ 140 ℃, and the reaction times is 2 ~ 5 hours; Wherein the mol ratio of cardanol, diethanolamine and formaldehyde is 1:1:1-1:3:3, oxyethane and propylene oxide for arbitrarily than and total mole number be 1-14 times of cardanol mole number.
4. the preparation method of biomass-based structure flame retardant type polyvalent alcohol according to claim 3, is characterized in that also comprising trimeric cyanamide or urea in Mannich reaction system, and the addition of trimeric cyanamide or urea is no more than 30% of cardanol weight.
5. according to the preparation method of biomass-based structure flame retardant type polyvalent alcohol described in claim 3 or 4, the mol ratio that it is characterized in that described cardanol, diethanolamine and formaldehyde is 1: 2: 2.
6. the preparation method of biomass-based structure flame retardant type polyvalent alcohol according to claim 4, the addition that it is characterized in that described trimeric cyanamide or urea is the 15-20% of cardanol weight.
7. the application of biomass-based structure flame retardant type polyvalent alcohol in preparing the flame-retardant polyurethane spray coating heat preservation material of pentamethylene foaming system described in claim 1 or 2.
8. the application of biomass-based structure flame retardant type polyvalent alcohol in preparation polyurethane foam described in claim 1 or 2.
9. the application of biomass-based structure flame retardant type polyvalent alcohol in preparation polyurethane foam according to claim 8, is characterized in that by mass parts, and preparation process is:
A. biomass-based structure flame retardant type polyvalent alcohol 50-100 part;
B. mixture 0.1-0.6 part of amines catalyst or amines catalyst and tin class catalyzer, wherein, amines catalyst is N, N, a kind of or any several mixture in-dimethylcyclohexylamine, triethylenediamine, dimethyl benzylamine, trolamine, α-amino isopropyl alcohol, quaternary amine, tin class catalyzer is di-n-butyltin dilaurate;
C. suds-stabilizing agent 0.5-5 part;
D. whipping agent 10-30 part, water 0.01-5 part;
By above-mentioned component mixing and stirring, then with isocyanic ester mix and blend 20-30s, rotating speed 3000-3500 r/min, pours in mould, slaking 48h, during foaming, isocyanic ester and polyvalent alcohol are 1.2～2.5 by the mol ratio of NCO/OH; Described isocyanic ester is tolylene diisocyanate, Xylene Diisocyanate or polymethine polyphenyl polyisocyanate.
10. biomass-based structure flame retardant type polyvalent alcohol application in polyurethane foam in preparation according to claim 9, is characterized in that also comprising in mixture the polyester polyol of hydroxyl value 250～450mgKOH/g, and consumption is no more than 50 parts.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4487852A (en) * | 1983-10-25 | 1984-12-11 | Texaco Inc. | Modified Mannich condensates and manufacture of rigid polyurethane foam with alkoxylation products thereof |
| CN102391492A (en) * | 2011-09-09 | 2012-03-28 | 上海桑迪精细化工研究所有限公司 | Preparation method of polyol for PU (polyurethane) hard bubble material with high oxygen index |
| CN102660014A (en) * | 2012-04-01 | 2012-09-12 | 耐素有限责任公司 | Cardanol polyether polyol and use thereof |
-
2013
- 2013-12-16 CN CN201310689200.8A patent/CN103709395B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4487852A (en) * | 1983-10-25 | 1984-12-11 | Texaco Inc. | Modified Mannich condensates and manufacture of rigid polyurethane foam with alkoxylation products thereof |
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