CN103755914B - A kind of preparation method of light stability polyurethane rigid foam plastic - Google Patents

A kind of preparation method of light stability polyurethane rigid foam plastic Download PDF

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Publication number
CN103755914B
CN103755914B CN201310703405.7A CN201310703405A CN103755914B CN 103755914 B CN103755914 B CN 103755914B CN 201310703405 A CN201310703405 A CN 201310703405A CN 103755914 B CN103755914 B CN 103755914B
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poly
rigid foam
foam plastic
polyurethane rigid
reactant
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CN201310703405.7A
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CN103755914A (en
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李荣华
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SUZHOU CITY WANTAI VACUUM FUENACE CO Ltd
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SUZHOU CITY WANTAI VACUUM FUENACE CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/724—Combination of aromatic polyisocyanates with (cyclo)aliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • 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
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0025—Foam properties rigid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00—Foam properties
    • C08G2110/0083—Foam properties prepared using water as the sole blowing agent

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention discloses the preparation method of a kind of light stability polyurethane rigid foam plastic, a, add the methyl iso-butyl ketone (MIBK) of metering being dried, in the reactor of cleaning, monohydroxy poly(ethylene oxide) and 1; 4 butanediols; the dibutyl tin laurate of catalytic amount, N, N dimethylformamide; tripolycyanamide; still is full of nitrogen or noble gas is protected, heat 40 ~ 60 DEG C, be sufficiently stirred for 3 ~ 6 hours; it is cooled to 25 DEG C, stand-by；B, the reactant liquor decompression distillation obtained in step a, reclaim organic solvent, obtain a polyether reactant thing；C, adding poly-4,4 ' '-diphenylmethane diisocyanates in reactant obtained above, poly-isophorone diisocyanate, light stabilizer, organic silicone oil, triethylamine, suitable quantity of water, high-speed stirred is to foaming；D, inject immediately in mould when a large amount of foams occur, ripening 50 ~ 180 minutes, the demoulding at 40 ~ 60 DEG C, obtain high-weathering-resistance polyurethane rigid foam plastic goods.

Description

A kind of preparation method of light stability polyurethane rigid foam plastic
Technical field
The present invention relates to plastic applications, particularly to the preparation method of a kind of light stability polyurethane rigid foam plastic.
Background technology
Polyurethane is the macromolecular compound with carbamate groups as repetitive generated with polyol reaction by polyisocyanates.Polyurethane resin has that soft durometer is adjustable, wear-resisting, solvent resistant, low temperature resistant and have the features such as stronger cementability with most of materials, development in recent years is rapid.nullHard polyurethane foams amount quick steady-state growth in the whole world in the past few decades，The data provided according to IAL report,Calendar year 2001 whole world polyurethane consumption be 987.6 ten thousand t wherein RPUF be 227.1 ten thousand t，Account for,23%，Within 2002, the whole world produces polyurethane products 1016.4 ten thousand t altogether，Sustainable development along with polyurethane industries among others，The demand average growth rate per annum of whole world polyurethane foam plastics is always held at about 7% at present，End 2010，World's polyurethane products yield is about 16,900,000 tons，According to relevant information，Hard polyurethane foam (RPUF) has excellent physical and mechanical properties、Electric property、Acoustical behavior and resistance to chemical corrosion，And with multiple material, there is the strongest cohesive force，Hard polyurethane foam is mainly used in cold preservation、Building heat preservation、Automobile and other industries，In recent years，Domestic due to construction wall、Aspect is incubated、Heat distribution pipeline、Oil field transport pipeline、Refrigerator and refrigerator-freezer insulation，Furniture、The fields such as door and window sheet material are widely applied，.Following along with the continuous expansion in building thermal-insulation energy-saving market, hard polyurethane foam demand is expected to welcome explosive growth, the field of hard bubbling is the demand bright spot of polyurethane industries among others maximum in future, it is contemplated that in the five-year, hard polyurethane foam will be with the speed increment of 15%～more than 20%.Conventional polyisocynate monomer mainly has 2,4-dimethyl diisocyanate (TDI), 4,4 '-'-diphenylmethane diisocyanate (MDI), owing to TDI, MDI contain rigidity aromatic ring, the cohesiveness making polyurethane is bigger, there is stronger hot strength, but the existence of aromatic ring can make foam plastics easily turn to be yellow, aging, fast light, weatherability is relatively low, plastic foam is become fragile by sun exposure and splits, the color and luster problems demand such as retreat in defeat solves, at present, domestic plastics in terms of synthesis with application technology compared with international most advanced level the biggest gap.
Summary of the invention
Goal of the invention: for defect of the prior art, it is provided that a kind of light resistance is strong, and production cost is relatively low, it is easy to the preparation method of the polyurethane rigid foam plastic of industrialized production.
The present invention is primary raw material by selecting MDI, it is ensured that product has bigger cohesiveness and stronger hot strength；Select another kind of raw material isophorone diisocyanate (IPDI) to be blended with MDI, and add light stabilizer, make product obtain preferable light weatherability, adjust each related raw material formula, technological operation, synthesize a kind of polyurethane rigid foam plastic with light stability.
For achieving the above object, the preparation method of a kind of light stability polyurethane rigid foam plastic, by the following technical solutions:
A, add the methyl iso-butyl ketone (MIBK) of metering being dried, in the reactor of cleaning; monohydroxy poly(ethylene oxide) and BDO, the dibutyl tin laurate of catalytic amount; N; dinethylformamide, tripolycyanamide, still is full of nitrogen or noble gas is protected; heat 40 ~ 60 DEG C; it is sufficiently stirred for 3 ~ 6 hours, is cooled to 25 DEG C, stand-by；
B, the reactant liquor decompression distillation obtained in step a, reclaim organic solvent, obtain a polyether reactant thing；
C, adding poly-4 in reactant obtained above, 4 '-'-diphenylmethane diisocyanate, poly-isophorone diisocyanate, light stabilizer, organic silicone oil, triethylamine, suitable quantity of water, high-speed stirred is to foaming；
D, inject immediately in mould when a large amount of foams occur, ripening 50 ~ 180 minutes, the demoulding at 40 ~ 60 DEG C, obtain high-weathering-resistance polyurethane rigid foam plastic goods.
Described light stabilizer is hindered amine light stabilizer, preferably light stabilizer 744(4-benzoyloxy-2,2,6,6-tetramethyl piperidines).
Described organic silicone oil be described hydroxy silicon oil be polydimethylsiloxane.
According to above technical scheme, it is possible to achieve following beneficial effect: the present invention made polyurethane light fastness is good, and validity period is greatly prolonged, and has and suitably draws high intensity and ductility, technological operation is simple, and cost is relatively low, is suitable for industrialized production.
Detailed description of the invention
Below in conjunction with embodiment the present invention done and describe in detail further, but the scope of protection of present invention is not limited to the scope that embodiment represents.
Embodiment 1:
The methyl iso-butyl ketone (MIBK) (100.0kg) of metering is added in reactor dry, that clean; monohydroxy poly(ethylene oxide) (300.0kg) and 1; 4-butanediol (85.0kg); dibutyl tin laurate (0.82kg); N; dinethylformamide (15.8kg); tripolycyanamide (65.0kg); still is full of nitrogen or noble gas is protected, heat 40 ~ 60 DEG C, be sufficiently stirred for 3 ~ 6 hours; it is cooled to 25 DEG C; the reactant liquor decompression distillation obtained, reclaims organic solvent, obtains a polyether reactant thing；
Poly-4 are added in reactant obtained above, 4 '-'-diphenylmethane diisocyanate (225.0kg), poly-isophorone diisocyanate (210.0kg), light stabilizer-744 (45.2kg), organic silicone oil polydimethylsiloxane (180.0kg), triethylamine (18.2kg), water (3.2kg), high-speed stirred is to foaming, inject immediately in mould when a large amount of foams occur, ripening 120 minutes, the demoulding at 40 ~ 60 DEG C, obtain high-weathering-resistance polyurethane rigid foam plastic goods.
Embodiment 2:
The methyl iso-butyl ketone (MIBK) (100.0kg) of metering is added in reactor dry, that clean; monohydroxy poly(ethylene oxide) (300.0kg) and 1; 4-butanediol (85.0kg); dibutyl tin laurate (0.89kg); N; dinethylformamide (15.8kg); tripolycyanamide (70.0kg); still is full of nitrogen or noble gas is protected, heat 40 ~ 60 DEG C, be sufficiently stirred for 3 ~ 6 hours; it is cooled to 25 DEG C; the reactant liquor decompression distillation obtained, reclaims organic solvent, obtains a polyether reactant thing；
Poly-4 are added in reactant obtained above, 4 '-'-diphenylmethane diisocyanate (215.0kg), poly-isophorone diisocyanate (200.0kg), light stabilizer-744 (46.6kg), organic silicone oil polydimethylsiloxane (185.0kg), triethylamine (18.2kg), water (3.2kg), high-speed stirred is to foaming, inject immediately in mould when a large amount of foams occur, ripening 120 minutes, the demoulding at 40 ~ 60 DEG C, obtain high-weathering-resistance polyurethane rigid foam plastic goods.
Embodiment 3:
The methyl iso-butyl ketone (MIBK) (100.0kg) of metering is added in reactor dry, that clean; monohydroxy poly(ethylene oxide) (300.0kg) and 1; 4-butanediol (85.0kg); dibutyl tin laurate (0.92kg); N; dinethylformamide (15.8kg); tripolycyanamide (75.0kg); still is full of nitrogen or noble gas is protected, heat 40 ~ 60 DEG C, be sufficiently stirred for 3 ~ 6 hours; it is cooled to 25 DEG C; the reactant liquor decompression distillation obtained, reclaims organic solvent, obtains a polyether reactant thing；
Poly-4 are added in reactant obtained above, 4 '-'-diphenylmethane diisocyanate (205.0kg), poly-isophorone diisocyanate (200.0kg), light stabilizer-744 (45.2kg), organic silicone oil polydimethylsiloxane (180.0kg), triethylamine (18.2kg), water (3.2kg), high-speed stirred is to foaming, inject immediately in mould when a large amount of foams occur, ripening 120 minutes, the demoulding at 40 ~ 60 DEG C, obtain high-weathering-resistance polyurethane rigid foam plastic goods.

Claims (1)

1. the preparation method of a light stability polyurethane rigid foam plastic, it is characterised in that by the following technical solutions:
A, add the methyl iso-butyl ketone (MIBK) of metering being dried, in the reactor of cleaning; monohydroxy poly(ethylene oxide) and BDO, the dibutyl tin laurate of catalytic amount; N; dinethylformamide, tripolycyanamide, still is full of nitrogen or noble gas is protected; heat 40 ~ 60 DEG C; it is sufficiently stirred for 3 ~ 6 hours, is cooled to 25 DEG C, stand-by；
B, the reactant liquor decompression distillation obtained in step a, reclaim organic solvent, obtain a polyether reactant thing；
C, adding poly-4 in reactant obtained above, 4 '-'-diphenylmethane diisocyanate, poly-isophorone diisocyanate, light stabilizer, organic silicone oil, triethylamine, suitable quantity of water, high-speed stirred is to foaming；
D, inject immediately in mould when a large amount of foams occur, ripening 50 ~ 180 minutes, the demoulding at 40 ~ 60 DEG C, obtain high-weathering-resistance polyurethane rigid foam plastic goods；Light stabilizer is 4-benzoyloxy-2,2,6,6-tetramethyl piperidines；Organic silicone oil is polydimethylsiloxane.
CN201310703405.7A 2013-12-20 2013-12-20 A kind of preparation method of light stability polyurethane rigid foam plastic Expired - Fee Related CN103755914B (en)

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JP7227347B2 (en) 2018-08-02 2023-02-21 ダウ グローバル テクノロジーズ エルエルシー Method for reducing aldehyde emissions of polyurethane foam
CN109734862A (en) * 2018-12-29 2019-05-10 广州市聚科聚氨酯有限公司 Utilize the method for modified isocyanate and combinations thereof production hard polyurethane foam

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102417581A (en) * 2011-11-01 2012-04-18 吴江市北厍盛源纺织品助剂厂 Preparation method for organic silicon modified polyurethane (PU) finishing agent
CN102417579A (en) * 2011-11-01 2012-04-18 吴江市北厍盛源纺织品助剂厂 Preparation method of yellowing-resistant polyurethane spinning coating agent

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DE102007023319A1 (en) * 2007-05-16 2008-11-20 Bayer Materialscience Ag Acidified polyester polyurethane dispersion

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102417581A (en) * 2011-11-01 2012-04-18 吴江市北厍盛源纺织品助剂厂 Preparation method for organic silicon modified polyurethane (PU) finishing agent
CN102417579A (en) * 2011-11-01 2012-04-18 吴江市北厍盛源纺织品助剂厂 Preparation method of yellowing-resistant polyurethane spinning coating agent

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