CN101693762B - Rosin polyether glycol used for flame-retardant hard polyurethane foaming plastic and preparation method thereof - Google Patents

Rosin polyether glycol used for flame-retardant hard polyurethane foaming plastic and preparation method thereof Download PDF

Info

Publication number
CN101693762B
CN101693762B CN2009101848727A CN200910184872A CN101693762B CN 101693762 B CN101693762 B CN 101693762B CN 2009101848727 A CN2009101848727 A CN 2009101848727A CN 200910184872 A CN200910184872 A CN 200910184872A CN 101693762 B CN101693762 B CN 101693762B
Authority
CN
China
Prior art keywords
flame
reaction
retardant
hard polyurethane
polyurethane foaming
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN2009101848727A
Other languages
Chinese (zh)
Other versions
CN101693762A (en
Inventor
周永红
张猛
胡立红
李书龙
刘红军
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu zhendiwang Energy Saving Technology Co.,Ltd.
Original Assignee
Institute of Chemical Industry of Forest Products of CAF
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Institute of Chemical Industry of Forest Products of CAF filed Critical Institute of Chemical Industry of Forest Products of CAF
Priority to CN2009101848727A priority Critical patent/CN101693762B/en
Publication of CN101693762A publication Critical patent/CN101693762A/en
Application granted granted Critical
Publication of CN101693762B publication Critical patent/CN101693762B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Abstract

The invention discloses a rosin polyether glycol used for flame-retardant hard polyurethane foaming plastic, with the structural formula that: R is n which equals to 1 to 10. A preparation method of the rosin polyether glycol comprises the following steps: adding rosin dibasic acid or tribasic acid, alkane diamine and acid catalyst in a pressure-resistant reaction kettle, mixing and stirring with temperature raised, reacting for 3 to 8 hours, reducing the temperature to 100 to 120 DEG C, adding base catalyst, keeping the temperature at 130 to 150 DEG C under the vacuumization and anaerobic condition, dividing oxirane and epoxypropane into a plurality of times, conducting alternate circular reaction according to the sequence of firstly introducing the oxirane and then introducing the epoxypropane, and conducting reduced pressure distillation after that to obtain a flame-retardant rosin polyether glycol. As the rosin polyether glycol contains rosin phenanthrene ring rigid structure, and contains a certain amount of flame-retardant nitrogen elements, when being used in hard polyurethane foaming plastic, the rosin polyether glycol has higher thermal stability and flame retardance, and good compression strength, with 28 to 30 percent the oxygen index, thus being used in building, heat insulation and a plurality of special fields.

Description

Used for flame-retardant hard polyurethane foaming plastic Rosinpolyether polylol and preparation method thereof
Technical field
The present invention relates to rosinyl used for flame-retardant hard polyurethane foaming plastic raw material and preparation technology thereof, particularly a kind of structure of Rosinpolyether polylol and preparation method, flame retardant type Rosinpolyether polylol are used to prepare the method for rigid urethane foam.
Background technology
Polyurethane foam is the present best heat-insulating material of performance in the world, because 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, and specific surface area is big, compares burning more easily with non-foam material, and burning and decomposition produce a large amount of toxic smogs.Meeting fire can burn and decompose, and hot burst size is big during burning, produces a large amount of toxic smogs, and HUMAN HEALTH and environment are all had very bad influence.Therefore, can the flame resistivity of rigid urethane foam, security have become the important technology index that be used for lagging material.National governments also promulgate a decree and rules in succession, stipulate that clearly under some occasion, the use of polyurethane material must reach certain flame-retardant standard, and the appearance of various rules has advanced the development of flame-retarded technology greatly.
The environmental-protection flame-retardant hard polyurethane foams product of exploitation Halogen, low cigarette, low toxicity has become the focus of people's research; In the molecular structure of inflammable amino-formate bond, introduce difficult combustion, heatproof, lowly be fuming, hypotoxicity heterocycle shape structural compounds is to solve the difficult combustion of PU, low smog, a hypotoxic technological line.The existence of this ring texture has improved foamy flame retardant resistance, temperature tolerance on the one hand greatly; Greatly reduce foam on the other hand and discharge smog toxicity.So response type heterocycle rigidity and halogen-free flameproof elements compounding flame retardant systems polyvalent alcohol are the focuses of studying at present.
USP 4214055,3953393 uses the fire-retardant polymerized polyalcohol of two or more mix monomer copolymerization in vinylchlorid, vinylidene chloride, vinylbenzene, the vinyl cyanide, and prepares resistance combustion polyurethane foam with it.But the homopolymer of Vilaterm, vinylidene chloride and multipolymer are unsettled, in foaming process, emit deleterious HCl gas, and foaming machine is had corrodibility; U.S. Pat 5250581 discloses with tribromo-benzene ethene and vinyl cyanide mix monomer copolymerization flame-proof polyol, and its urethane foam that makes has certain flame retardant resistance, but tribromo-benzene ethene synthesizes difficulty, price is high and contain halogen.Patent 200710021640.0 discloses and has been used for Rosinpolyether polylol of rigid urethane foam and preparation method thereof, comprises the structure of Rosinpolyether polylol and the preparation method of rosinyl hard polyurethane foams; But this polyvalent alcohol does not contain fire-retardant nitrogen element, and the oxygen index of the rigid urethane foam of processing is not high, and flame retardant effect is more general.
Summary of the invention
The purpose of this invention is to provide a kind of used for flame-retardant hard polyurethane foaming plastic Rosinpolyether polylol and preparation method thereof, adopt structurally-modified method, introduce rosin ternary phenanthrene ring flame resisting construction and fire-retardant nitrogen element in the polyol structure; Obtain having the reaction-type flame-retarding polyvalent alcohol of composite flame-proof system.
Technical scheme of the present invention is: a kind of used for flame-retardant hard polyurethane foaming plastic Rosinpolyether polylol, structural formula is: wherein R is
N=1~10, R is the epoxyethane ring-expansion polymerization thing of continuous multi-stage and the polymkeric substance of the alternate formation of propylene oxide ring-opening polymerization polymer, n can control through oxyethane, the each feeding amount of propylene oxide.
The preparation method of described used for flame-retardant hard polyurethane foaming plastic Rosinpolyether polylol is to adopt structurally-modified method, introduces rosin ternary phenanthrene ring flame resisting construction and fire-retardant nitrogen element in the polyol structure; Obtain having the reaction-type flame-retarding Rosinpolyether polylol of composite flame-proof system, reaction equation is:
Concrete grammar is:
Acid catalyst with 400-500 mass parts rosin diprotic acid or triprotic acid, 150-250 mass parts alkane diamines, 1-10 mass parts adds withstand voltage reaction kettle, and mixing heats up stirs; Reaction is 3-8 hour under 160-200 ℃, pressure 0.2-0.6MPa condition, cools to 100-120 ℃, adds 0.1-5 mass parts alkaline catalysts; Vacuumize under the oxygen free condition, make temperature be in 130-150 ℃ again, the oxyethane of 50-500 mass parts and the propylene oxide branch of 50-500 mass parts are made several times; According to feeding the order that oxyethane feeds propylene oxide more earlier, alternate cycles feeds, after feeding each time; React 30-60min, and reaction pressure is remained on 0.3-1.0MPa, after reaction finishes; Underpressure distillation obtains the flame retardant type Rosinpolyether polylol.
Wherein, described rosin diprotic acid or triprotic acid be in maleopimaric acid, maleopimaric anhydride, the rosin acrylic acid any one or any several kinds arbitrarily than mixture, preferred maleopimaric anhydride.Described alkane diamines is any in urea, quadrol, tn, hexanediamine, the decamethylene diamine, preferred quadrol.Described acid catalyst is any one in tosic acid, sulfuric acid, hydrochloric acid, the phosphoric acid, preferred tosic acid.Described alkaline catalysts is any one in KOH, NaOH, potassium methylate, the USP Kosher potassium.
Described used for flame-retardant hard polyurethane foaming plastic Rosinpolyether polylol can prepare flame-retardant hard polyurethane foaming plastic, and method foams in the presence of auxiliary agent and prepares the rosinyl flame-retardant hard polyurethane foaming plastic for the Rosinpolyether polylol that will be described be used for flame-retardant hard polyurethane foaming plastic and general polyethers or polyester polyol, isocyanate compound.
Being prepared as of concrete rosinyl flame-retardant hard polyurethane foaming plastic:
1, earlier by following formulated combination polyvalent alcohol, in mass parts:
1. the used for flame-retardant hard polyurethane foaming plastic Rosinpolyether polylol (be called for short: the 50-100 part flame retardant type Rosinpolyether polylol) by the back;
2. polyester or polyether glycol 0-50 part (hydroxyl value 250~450mgKOH/g), preferred benzoic anhydride polyester polyol, rosin polyester polyhydric-alcohol, polyether glycol 635, polyether glycol 450;
3. catalyzer 0.1-3 part is generally composite catalyst; Can be amines catalyst or amines catalyst and tin class mixture of catalysts.Wherein, Amines catalyst is selected from: N, N ,-dimethylcyclohexylamine, triethylenediamine, dimethyl benzylamine, trolamine, Yi Bingchunan, quaternary amine or similar catalyzer; Can be one of above-mentioned substance, also can two or more mixtures with arbitrary proportion.Tin class catalyzer is selected from: di-n-butyltin dilaurate and similar catalyzer.
4. suds-stabilizing agent 0.5-5 part mainly is silicon-oxygen or silicon-charcoal type tensio-active agent, and dolantin generation wound 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 also can be that two or more arbitrary proportion mixes and uses.
5. whipping agent 10-30 part: HCFC-141b, pentamethylene, iso-pentane, HFC-245fa, HFC-365mfc, etc. choose any one kind of them or multiple mixture with arbitrary proportion; Water 0.01-5 part.
2, the prescription of flame-retardant hard polyurethane foaming plastic and preparation:
Flame-retardant hard polyurethane foaming plastic is according to the formulated of table 1, and the performance measurement result sees table 2.(NCO/OH is 1.2~2.5).
Concrete operations are following: be uniformly dispersed combination polyvalent alcohol high-speed stirring earlier, mix high-speed stirring 20-30s again with isocyanic ester, rotating speed 3000-3500r/min pours in the mould, slaking 48h.
Beneficial effect:
1. the flame retardant type Rosinpolyether polylol is to adopt structurally-modified method, introduces rosin ternary phenanthrene ring flame resisting construction and fire-retardant nitrogen element in the polyol structure; Obtain having the reaction-type flame-retarding polyvalent alcohol of composite flame-proof system; Be used for synthetic flame-retardant hard polyurethane foaming plastic, it has higher thermostability and flame retardant resistance, good compressive strength, and oxygen index 28-30%, what have reaches more than 30%.Be with a wide range of applications at building, insulation and some special occasions.
2. the more general petrochemical industry class polyether glycol of reactive behavior, emulsifying property of in foam application, finding the flame retardant type Rosinpolyether polylol will be got well.
3. rosin is renewable resources, environmental protection, does not receive the influence of oil price, cost low.
Description of drawings
The ir spectra of Fig. 1 used for flame-retardant hard polyurethane foaming plastic Rosinpolyether polylol
Ir spectra by Fig. 1 used for flame-retardant hard polyurethane foaming plastic Rosinpolyether polylol can be known 3445cm -1Vibration absorption peak for vOH or vNH; 2975cm -1, 2878cm -1Stretching vibration absorption peak for methyl, methylene radical; 1725cm -1Absorption peak for carbonyl C=O; 1648cm -1Stretching vibration absorption peak for the vC=C on the rosin ring; 1469cm -1, 1386cm -1Charateristic avsorption band for humorous dimethylated δ CH on the rosin ring sec.-propyl; 1330cm -1It possibly be the absorption peak of the III band of vNH; 1258cm -1Stretching vibration absorption peak for terminal hydroxy group vC-O; 1110cm -1Strong stretching vibration absorption peak for vC-O-C.
The ir spectra of the flame retarded rigid polyurethane foams plastics after the modification of Fig. 2 used for flame-retardant hard polyurethane foaming plastic Rosinpolyether polylol
Learn by Fig. 2: 3420cm -1Be the cis NH stretching vibration of vOH stretching vibration, NHCO, 2929cm -12876cm -1Be respectively CH 3, CH 2Stretching vibration, 2277cm -1Be NCO charateristic avsorption band, 2127cm -1Be N=C=N absorption peak, 1721cm -1Be ester group C=O, acid amides I key (C=O), 1605cm -1Be phenyl ring C=C skeleton stretching vibration, 1525cm -1Be acid amides II key (N-H formation vibration), 1456cm -1Be CH 2Formation vibration, CH 3The asymmetrical deformation vibration, 1383cm -1Be CH 3Symmetrical deformation vibration, 1233cm -1For ester bond C-O stretches or the OH formation vibration; 1086cm -1Be the strong stretching vibration peak of vC-O-C, 1421cm -1Absorption peak for isocyanuric acid ester.
Embodiment
Be described further with specific embodiment below: raw materials usedly among the present invention be all commercially availablely, each raw material all is in mass parts.
Embodiment 1.
With 400 parts of maleopimaric acids, 150 parts of quadrols, 5 parts of tosic acid, add withstand voltage reaction kettle, mixing heats up stirs, and at 180 ℃, pressure keeps 0.4Mpa, reaction 6 hours, cools to 100 ℃, adds 1 part of KOH, vacuumizes N 2Gas displacement 3 times; Be warmed up to 150 ℃, 500 parts of oxyethane, 500 parts of propylene oxide equivalent alternate cycles are fed, the reacting ethylene oxide that just feeds a part earlier is after for some time; Feed the propylene oxide of equal in quality again, alternate cycles feeds and finishes until total overall reaction like this.150 ℃ of temperature of reaction, reaction pressure 1.0MPa reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 60min.Lead to the epoxide afterreaction and finished stopped reaction, emptying.At 120 ℃/10mm Hg; The 30min that finds time reduces pressure; Obtain the flame retardant type Rosinpolyether polylol, structural formula is: wherein R is
N=1~10, R is the epoxyethane ring-expansion polymerization thing of continuous multi-stage and the polymkeric substance of the alternate formation of propylene oxide ring-opening polymerization polymer, n can control through oxyethane, the each feeding amount of propylene oxide.
Preparation prescription according to table 1 rigid urethane foam obtains making up polyvalent alcohol then, and high-speed stirring is even, mixes high-speed stirring 20-30s again with isocyanic ester, and rotating speed 3000-3500r/min pours in the mould, slaking 48h.
Embodiment 2.
With 450 parts of maleopimaric acids, 200 parts of quadrols, 2 parts of sulfuric acid, add withstand voltage reaction kettle, mixing heats up stirs, and at 170 ℃, pressure keeps 0.8Mpa, reaction 4 hours, cools to 110 ℃, adds 1 part of KOH, vacuumizes N 2Gas displacement 3 times is warmed up to 150 ℃, and the equivalent circulation feeds 300 parts of oxyethane, 400 parts of propylene oxide.140 ℃ of temperature of reaction, reaction pressure 0.8MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 60min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time that reduces pressure obtains the flame retardant type Rosinpolyether polylol.Preparation prescription according to table 1 rigid urethane foam obtains making up polyvalent alcohol then, and high-speed stirring is even, mixes high-speed stirring 20-30s again with isocyanic ester, and rotating speed 3000-3500r/min pours in the mould, slaking 48h.
Embodiment 3.
With 480 parts of maleopimaric anhydrides, 250 parts of urea, 4 parts of phosphoric acid, add withstand voltage reaction kettle, mixing heats up stirs, and at 160 ℃, pressure keeps 0.3Mpa, reaction 7 hours, cools to 120 ℃, adds 3 parts of potassium methylates, vacuumizes N 2Gas displacement 3 times is warmed up to 140 ℃, and the equivalent circulation feeds 100 parts of oxyethane, 300 parts of propylene oxide.140 ℃ of temperature of reaction, reaction pressure 0.5MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 60min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time that reduces pressure obtains the flame retardant type Rosinpolyether polylol.Preparation prescription according to table 1 rigid urethane foam obtains making up polyvalent alcohol then, and high-speed stirring is even, mixes high-speed stirring 20-30s again with isocyanic ester, and rotating speed 3000-3500r/min pours in the mould, slaking 48h.
Embodiment 4.
With 400 parts of rosin acrylic acids, 180 parts of tn, 5 parts of tosic acid, add withstand voltage reaction kettle, mixing heats up stirs, and at 190 ℃, pressure keeps 0.5Mpa, reaction 4 hours, cools to 110 ℃, adds 2 parts of NaOH, vacuumizes N 2Gas displacement 3 times is warmed up to 130 ℃, and the equivalent circulation feeds 50 parts of oxyethane, 500 parts of propylene oxide.140 ℃ of temperature of reaction, reaction pressure 0.6MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 60min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time that reduces pressure obtains the flame retardant type Rosinpolyether polylol.Preparation prescription according to table 1 rigid urethane foam obtains making up polyvalent alcohol then, and high-speed stirring is even, mixes high-speed stirring 20-30s again with isocyanic ester, and rotating speed 3000-3500r/min pours in the mould, slaking 48h.
Embodiment 5.
With 500 parts of maleopimaric anhydrides, 250 parts of hexanediamines, 4 parts of hydrochloric acid, add withstand voltage reaction kettle, mixing heats up stirs, and at 200 ℃, pressure keeps 0.6Mpa, reaction 5 hours, cools to 110 ℃, adds 3 parts of USP Kosher potassium, vacuumizes N 2Gas displacement 3 times is warmed up to 150 ℃, and the equivalent circulation feeds 100 parts of oxyethane, 250 parts of propylene oxide.150 ℃ of temperature of reaction, reaction pressure 0.3MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 60min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time that reduces pressure obtains the flame retardant type Rosinpolyether polylol.Preparation prescription according to table 1 rigid urethane foam obtains making up polyvalent alcohol then, and high-speed stirring is even, mixes high-speed stirring 20-30s again with isocyanic ester, and rotating speed 3000-3500r/min pours in the mould, slaking 48h.
Embodiment 6.
With 400 parts of maleopimaric acids, 180 parts of decamethylene diamines, 1 part of phosphoric acid, add withstand voltage reaction kettle, mixing heats up stirs, and at 180 ℃, pressure keeps 0.4Mpa, reaction 3 hours, cools to 100 ℃, adds 5 parts of potassium methylates, vacuumizes N 2Gas displacement 3 times is warmed up to 140 ℃, and the equivalent circulation feeds 50 parts of oxyethane, 150 parts of propylene oxide.140 ℃ of temperature of reaction, reaction pressure 0.7MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 60min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time that reduces pressure obtains the flame retardant type Rosinpolyether polylol.Preparation prescription according to table 1 rigid urethane foam obtains making up polyvalent alcohol then, and high-speed stirring is even, mixes high-speed stirring 20-30s again with isocyanic ester, and rotating speed 3000-3500r/min pours in the mould, slaking 48h.
Embodiment 7.
With 400 parts of rosin acrylic acids, 250 parts of pentamethylene diamines, 5 parts of tosic acid, add withstand voltage reaction kettle, mixing heats up stirs, and at 200 ℃, pressure keeps 0.7Mpa, reaction 7 hours, cools to 120 ℃, adds 3 parts of KOH, vacuumizes N 2Gas displacement 3 times is warmed up to 150 ℃, and the equivalent circulation feeds 150 parts of oxyethane, 100 parts of propylene oxide.150 ℃ of temperature of reaction, reaction pressure 0.3MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 60min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time that reduces pressure obtains the flame retardant type Rosinpolyether polylol.Preparation prescription according to table 1 rigid urethane foam obtains making up polyvalent alcohol then, and high-speed stirring is even, mixes high-speed stirring 20-30s again with isocyanic ester, and rotating speed 3000-3500r/min pours in the mould, slaking 48h.
Embodiment 8.
With 480 parts of maleopimaric anhydrides, 150 parts of quadrols, 4 parts of tosic acid, add withstand voltage reaction kettle, mixing heats up stirs, and at 160 ℃, pressure keeps 0.5Mpa, reaction 4 hours, cools to 110 ℃, adds 1 part of USP Kosher potassium, vacuumizes N 2Gas displacement 3 times is warmed up to 130 ℃, and the equivalent circulation feeds 250 parts of oxyethane, 300 parts of propylene oxide.140 ℃ of temperature of reaction, reaction pressure 0.5MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 60min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time that reduces pressure obtains the flame retardant type Rosinpolyether polylol.Preparation prescription according to table 1 rigid urethane foam obtains making up polyvalent alcohol then, and high-speed stirring is even, mixes high-speed stirring 20-30s again with isocyanic ester, and rotating speed 3000-3500r/min pours in the mould, slaking 48h.
Embodiment 9.
Hydrochloric acid with 300 parts of maleopimaric acids and 150 parts of rosin acrylic acids, 180 parts of hexanediamines, 4 parts of quality adds withstand voltage reaction kettle, and mixing heats up stirs, and at 180 ℃, pressure keeps 0.7Mpa, reaction 3 hours, cools to 120 ℃, adds 1 part of NaOH, vacuumizes N 2Gas displacement 3 times is warmed up to 150 ℃, and the equivalent circulation feeds 200 parts of oxyethane, 300 parts of propylene oxide.150 ℃ of temperature of reaction, reaction pressure 0.4MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 60min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time that reduces pressure obtains the flame retardant type Rosinpolyether polylol.Preparation prescription according to table 1 rigid urethane foam obtains making up polyvalent alcohol then, and high-speed stirring is even, mixes high-speed stirring 20-30s again with isocyanic ester, and rotating speed 3000-3500r/min pours in the mould, slaking 48h.
Embodiment 10.
Tosic acid with 400 parts of maleopimaric anhydrides and 100 parts of rosin acrylic acids, 250 parts of quadrols, 3 parts of quality adds withstand voltage reaction kettle, and mixing heats up stirs; At 190 ℃, pressure keeps 0.5Mpa, reaction 5 hours, cools to 110 ℃; Add 3 parts of KOH, vacuumize N 2Gas displacement 3 times is warmed up to 140 ℃, and the equivalent circulation feeds 50 parts of oxyethane, 350 parts of propylene oxide.150 ℃ of temperature of reaction, reaction pressure 0.9MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 60min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time that reduces pressure obtains the flame retardant type Rosinpolyether polylol.Preparation prescription according to table 1 rigid urethane foam obtains making up polyvalent alcohol then, and high-speed stirring is even, mixes high-speed stirring 20-30s again with isocyanic ester, and rotating speed 3000-3500r/min pours in the mould, slaking 48h.
Embodiment 11.
Sulfuric acid with 300 parts of maleopimaric acids and 150 parts of maleopimaric anhydrides, 180 parts of urea, 4 parts of quality adds withstand voltage reaction kettle, and mixing heats up stirs, and at 160 ℃, pressure keeps 0.4Mpa, reaction 6 hours, cools to 100 ℃, adds 1 part of potassium methylate, vacuumizes N 2Gas displacement 3 times is warmed up to 150 ℃, and the equivalent circulation feeds 350 parts of oxyethane, 500 parts of propylene oxide.140 ℃ of temperature of reaction, reaction pressure 0.7MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 60min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 120 ℃/10mm Hg, the 30min that finds time that reduces pressure obtains the flame retardant type Rosinpolyether polylol.Preparation prescription according to table 1 rigid urethane foam obtains making up polyvalent alcohol then, and high-speed stirring is even, mixes high-speed stirring 20-30s again with isocyanic ester, and rotating speed 3000-3500r/min pours in the mould, slaking 48h.
Embodiment 12.
Tosic acid with 200 parts of maleopimaric acids, 150 parts of maleopimaric anhydrides, 150 parts of rosin acrylic acids, 250 parts of quadrols, 5 parts of quality adds withstand voltage reaction kettle, and mixing heats up stirs; Keep 0.6Mpa, reaction 5 hours at 190 ℃, pressure; Cool to 110 ℃, add 5 parts of KOH, vacuumize N2 gas displacement 3 times; Be warmed up to 150 ℃, the equivalent circulation feeds 250 parts of oxyethane, 50 parts of propylene oxide.130 ℃ of temperature of reaction, reaction pressure 0.6MP reaction.When equivalent circulation feeds oxyethane, propylene oxide, led to epoxide each time after, constant reaction 60min.Having led to the epoxide afterreaction finishes.Stopped reaction.Emptying.At 130 ℃/10mm Hg, the 30min that finds time reduces pressure.Preparation prescription according to table 1 rigid urethane foam obtains making up polyvalent alcohol then, and high-speed stirring is even, mixes high-speed stirring 20-30s again with isocyanic ester, and rotating speed 3000-3500r/min pours in the mould, slaking 48h.
The preparation dispensing information of rigid urethane foam:
Catalyzer: be generally composite catalyst; Can be amines catalyst or amines catalyst and tin class mixture of catalysts.Wherein, Amines catalyst is selected from: N, N ,-dimethylcyclohexylamine, triethylenediamine, dimethyl benzylamine, trolamine, Yi Bingchunan, quaternary amine or similar catalyzer; Can be one of above-mentioned substance, also can two or more mixtures with arbitrary proportion.Tin class catalyzer is selected from: di-n-butyltin dilaurate and similar catalyzer.
Suds-stabilizing agent: mainly be silicon-oxygen or silicon-charcoal type tensio-active agent, dolantin generation wound 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 also can be that two or more arbitrary proportion mixes and uses.
Whipping agent: HCFC-141b, pentamethylene, iso-pentane, HFC-245fa, HFC-365mfc etc. choose any one kind of them or multiple mixture with arbitrary proportion.Weight ratio 100: 0~30 when the combination polyvalent alcohol mixes with whipping agent.
Isocyanic ester can be selected from: tolylene diisocyanate, XDI, polymethine polyphenyl polyisocyanate (PAPI), and preferred PAPI, trade names are: the Desmodur N of Bayer company, 44V20L, 44V10L etc.; Huntsman Corporation's Super ace5005,2085 etc.; The PAPI27 of DOW company; The MR200 of BASF AG; The PM2010 of Yantai Wan Hua company etc.Isocyanic ester and combined polyether (ester) are 1.2~2.5 by the mol ratio of NCO/OH during foaming.
Table 2 is the performance measurement result of rigid urethane foam after the modification
The prescription (part) of table 1 embodiment 1~12 combination polyvalent alcohol
Table 2 urethane foam product performance (testing method is with reference to national standard)
Mensuration shows: the flame retardant type Rosinpolyether polylol for preparing with the present invention replaces common polyvalent alcohol by mass parts 50~100, obtains the rigid urethane foam sample, has good mechanical property, thermostability and flame retardant resistance; Oxygen index 28-30%, what have reaches more than 30%.Can in higher envrionment temperature, use, heat insulation effect is improved, and has practiced thrift the energy.

Claims (4)

1. the preparation method of a used for flame-retardant hard polyurethane foaming plastic Rosinpolyether polylol is characterized in that, adopts structurally-modified method, introduces rosin ternary phenanthrene ring flame resisting construction and fire-retardant nitrogen element in the polyol structure; Obtain having the reaction-type flame-retarding Rosinpolyether polylol of composite flame-proof system, concrete grammar is:
Acid catalyst with 400-500 mass parts maleopimaric acid, 150-250 mass parts quadrol, 1-10 mass parts adds withstand voltage reaction kettle, and mixing heats up stirs; Reaction is 3-8 hour under 160-200 ℃, pressure 0.2-0.6MPa condition, cools to 100-120 ℃, adds 0.1-5 mass parts alkaline catalysts; Vacuumize under the oxygen free condition, make temperature be in 130-150 ℃ again, the oxyethane of 50-500 mass parts and the propylene oxide branch of 50-500 mass parts are made several times; According to feeding the order that oxyethane feeds propylene oxide more earlier, alternate cycles feeds, after feeding each time; React 30-60min, and reaction pressure is remained on 0.3-1.0MPa, after reaction finishes; Underpressure distillation obtains the flame retardant type Rosinpolyether polylol;
The structural formula of described flame retardant type Rosinpolyether polylol is:
wherein R does
n=1~10。
2. the preparation method of used for flame-retardant hard polyurethane foaming plastic Rosinpolyether polylol as claimed in claim 1 is characterized in that, described acid catalyst is any one in tosic acid, sulfuric acid, hydrochloric acid, the phosphoric acid.
3. the preparation method of used for flame-retardant hard polyurethane foaming plastic Rosinpolyether polylol as claimed in claim 1 is characterized in that, described alkaline catalysts is any one in KOH, NaOH, potassium methylate, the USP Kosher potassium.
4. based on the application of used for flame-retardant hard polyurethane foaming plastic Rosinpolyether polylol in preparing the method for flame-retardant hard polyurethane foaming plastic of the preparation method of the described used for flame-retardant hard polyurethane foaming plastic Rosinpolyether polylol of claim 1 preparation; It is characterized in that described Rosinpolyether polylol that is used for flame-retardant hard polyurethane foaming plastic and general polyethers or polyester polyol, the isocyanate compound preparation rosinyl flame-retardant hard polyurethane foaming plastic that in the presence of auxiliary agent, foams.
CN2009101848727A 2009-10-16 2009-10-16 Rosin polyether glycol used for flame-retardant hard polyurethane foaming plastic and preparation method thereof Active CN101693762B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN2009101848727A CN101693762B (en) 2009-10-16 2009-10-16 Rosin polyether glycol used for flame-retardant hard polyurethane foaming plastic and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN2009101848727A CN101693762B (en) 2009-10-16 2009-10-16 Rosin polyether glycol used for flame-retardant hard polyurethane foaming plastic and preparation method thereof

Publications (2)

Publication Number Publication Date
CN101693762A CN101693762A (en) 2010-04-14
CN101693762B true CN101693762B (en) 2012-07-25

Family

ID=42092767

Family Applications (1)

Application Number Title Priority Date Filing Date
CN2009101848727A Active CN101693762B (en) 2009-10-16 2009-10-16 Rosin polyether glycol used for flame-retardant hard polyurethane foaming plastic and preparation method thereof

Country Status (1)

Country Link
CN (1) CN101693762B (en)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101891883B (en) * 2010-06-25 2012-07-18 中国林业科学研究院林产化学工业研究所 Rosin polyester polyol for flame-retardant rigid polyurethane foam plastic and preparation method and application thereof
CN102002157B (en) * 2010-08-13 2012-07-04 上海东大聚氨酯有限公司 Aromatic polyester modified polyether polyol and preparation method thereof
CN105542145B (en) * 2016-02-22 2017-08-25 中国林业科学研究院林产化学工业研究所 A kind of citrate ether polymerized polyalcohol and its preparation method and application
CN106519157B (en) * 2016-10-25 2019-02-19 中国林业科学研究院林业新技术研究所 Structure flame retardant Rosin-based Polyol and its preparation method and application for hard polyurethane foams
EP3549969A1 (en) * 2018-04-06 2019-10-09 Covestro Deutschland AG Polyurethane foams based on polyether carbonate polyols
CN109868066A (en) * 2018-08-28 2019-06-11 中国林业科学研究院林产化学工业研究所 Abietyl CO2/N2Response type surfactant and preparation method and purposes
CN110423353B (en) * 2019-08-14 2022-03-01 中国林业科学研究院林产化学工业研究所 Polysiloxane, maleopimaric acid modified polysiloxane and maleopimaric acid modified polysiloxane flame-retardant polyurethane foam

Also Published As

Publication number Publication date
CN101693762A (en) 2010-04-14

Similar Documents

Publication Publication Date Title
CN101693762B (en) Rosin polyether glycol used for flame-retardant hard polyurethane foaming plastic and preparation method thereof
CN101891883B (en) Rosin polyester polyol for flame-retardant rigid polyurethane foam plastic and preparation method and application thereof
CN102050945B (en) Polyether glycol, polyurethane rigid foamed plastic and preparation methods thereof
CN103319675B (en) Castor oil-base flame-proof polyol composition and method of making the same and application
US4426461A (en) Modified polyisocyanurate foam and method of preparation
CN103709395A (en) Biomass base structure flame retardant polyol and preparation method and application thereof
CN104877105B (en) A kind of polyurethane hard bubble composite material and preparation method thereof
EP1115771B1 (en) Rigid polyurethane foam and heat insulating construction element comprising the same
CN103382266A (en) Polyurethane foam fire retardant, and preparation method and applications thereof
CN106543426B (en) A kind of siliceous flame retardant type Rosin-based Polyol and its preparation method and application
CN103391954B (en) High temperature resistant foamed materials
CN102070412B (en) Flame-retardant polyether glycol and preparation method thereof, combined polyether and polyurethane foam
CN107033317A (en) A kind of hard polyurethane foam material and preparation method and application
CN102167898A (en) Environment-friendly composite material applied to heat preservation of pipeline and preparation method thereof
CN101045785B (en) Rosinpolyether polylol for hard polyurethane foam plastic and preparation method thereof
CN101792152B (en) Abietyl quaternary ammonium salt-modified organic nano imvite, preparation method thereof and use thereof
CN105524245A (en) High-toughness flame-retardant hard polyurethane foam board
CN104927022A (en) Halogen-free inherent flame retardant type RPUF (Rigid Polyurethane Foam) and preparation method thereof
RU2222550C2 (en) Jointly initiated polyether-polyol and a method for preparation thereof
CN106279630A (en) Floride-free type polyurethane insulation material
CN102432850A (en) Method for preparing structure type flame-retardant castor-oil-based polyester polyol and applications thereof
CN105461895A (en) Premixed polyether polyol, polyisocyanurate foam, as well as raw material composition and preparation method of polyisocyanurate foam
FI77676C (en) FOERFARANDE FOER FRAMSTAELLNING AV ETT ISOCYANURATMODIFIERAT POLYURETANSKUM OCH MEDELST FOERFARANDET FRAMSTAELLT POLYURETANSKUM.
CN102532865B (en) Composite polyether for environmentally-friendly open pore type pipeline and preparation method thereof
CN106188463A (en) The polyurethane resin insulation material of high-hydroscopicity

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20181212

Address after: 277500 No. 218 Xingye South Road, Tengzhou Economic Development Zone, Zaozhuang City, Shandong Province

Patentee after: Shandong Huaaosi New Building Material Co., Ltd.

Address before: No. 16, No. five village, lock gold, Nanjing, Jiangsu

Patentee before: Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20201223

Address after: 277500 Liandi business center, south of Tengzhou high speed railway station, Zaozhuang City, Shandong Province

Patentee after: Shangpin Bense smart home Co.,Ltd.

Address before: 277500 No. 218 Xingye South Road, Tengzhou Economic Development Zone, Zaozhuang City, Shandong Province

Patentee before: SHANDONG HUAAOSI NEW BUILDING MATERIAL Co.,Ltd.

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20210727

Address after: 221011 south side of Xujia fast track, Jiangsu Xuzhou Industrial Park, Jiawang District, Xuzhou City, Jiangsu Province

Patentee after: Xuzhou Jinglin Institute of new biomaterials Technology Co.,Ltd.

Address before: 277500 Liandi business center, south of Tengzhou high speed railway station, Zaozhuang City, Shandong Province

Patentee before: Shangpin Bense smart home Co.,Ltd.

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20210907

Address after: 221011 west side of Xinxi flood discharge Road, north side of tuntou Industrial Park, Jiawang District, Xuzhou City, Jiangsu Province

Patentee after: Jiangsu zhendiwang Energy Saving Technology Co.,Ltd.

Address before: 221011 south side of Xujia fast track, Jiangsu Xuzhou Industrial Park, Jiawang District, Xuzhou City, Jiangsu Province

Patentee before: Xuzhou Jinglin Institute of new biomaterials Technology Co.,Ltd.