CN115109309A - Method for improving storage stability of polyurethane prepolymer - Google Patents
Method for improving storage stability of polyurethane prepolymer Download PDFInfo
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- CN115109309A CN115109309A CN202110299961.7A CN202110299961A CN115109309A CN 115109309 A CN115109309 A CN 115109309A CN 202110299961 A CN202110299961 A CN 202110299961A CN 115109309 A CN115109309 A CN 115109309A
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000003860 storage Methods 0.000 title claims abstract description 25
- 229920001730 Moisture cure polyurethane Polymers 0.000 title claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 27
- 239000010452 phosphate Substances 0.000 claims abstract description 27
- 239000000654 additive Substances 0.000 claims abstract description 25
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract 2
- -1 phosphate ester Chemical class 0.000 claims description 17
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 125000006353 oxyethylene group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 22
- 229920005862 polyol Polymers 0.000 description 16
- 150000003077 polyols Chemical class 0.000 description 16
- 239000004721 Polyphenylene oxide Substances 0.000 description 14
- 229920000570 polyether Polymers 0.000 description 14
- 230000006866 deterioration Effects 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 5
- AVWRKZWQTYIKIY-UHFFFAOYSA-N urea-1-carboxylic acid Chemical compound NC(=O)NC(O)=O AVWRKZWQTYIKIY-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 229920001971 elastomer Polymers 0.000 description 4
- 239000000806 elastomer Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000003760 hair shine Effects 0.000 description 3
- 229920005906 polyester polyol Polymers 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229920005830 Polyurethane Foam Polymers 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- UHGIMQLJWRAPLT-UHFFFAOYSA-N octadecyl dihydrogen phosphate Chemical compound CCCCCCCCCCCCCCCCCCOP(O)(O)=O UHGIMQLJWRAPLT-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000011496 polyurethane foam Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LFSYUSUFCBOHGU-UHFFFAOYSA-N 1-isocyanato-2-[(4-isocyanatophenyl)methyl]benzene Chemical class C1=CC(N=C=O)=CC=C1CC1=CC=CC=C1N=C=O LFSYUSUFCBOHGU-UHFFFAOYSA-N 0.000 description 1
- TVAJJUOMNRUGQA-UHFFFAOYSA-N 2-butoxyethyl dihydrogen phosphate Chemical compound CCCCOCCOP(O)(O)=O TVAJJUOMNRUGQA-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- SNAMIIGIIUQQSP-UHFFFAOYSA-N bis(6-methylheptyl) hydrogen phosphate Chemical compound CC(C)CCCCCOP(O)(=O)OCCCCCC(C)C SNAMIIGIIUQQSP-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000012939 laminating adhesive Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
Landscapes
- 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 provides a method for improving the storage stability of a prepolymer, which is realized by adding an effective amount of additives into a system, wherein the additives comprise a) phosphate and b) a silane coupling agent. The phosphate is at least one selected from the group consisting of compounds represented by the following chemical formulae (I), (II), and (III):
wherein, in the formula (I), R 1 、R 2 Identical or different, are each a hydrogen atom, a hydrocarbon group or an aryl group, R 1 And R 2 At least one of which is a hydrocarbyl or aryl group; in the formulae (II) and (III), R 3 And R 4 Identical or different, are each a hydrogen atom, a hydrocarbon group or an aryl group, R 3 And R 4 At least one of them is a hydrocarbon group or an aryl group, AO is an alkylene oxide group, and n represents an integer of 1 or more. The silane coupling agent is at least one of KH550, KH792 and KH 602. The additive can stably exist in MDI and play a role in the synthesis and storage processes of the prepolymer, thereby being beneficial to improving the storage stability of the prepolymer.
Description
Technical Field
The invention relates to the field of isocyanate, in particular to a method for improving the storage stability of a polyurethane prepolymer.
Background
MDI can be applied to NCO-terminated prepolymers for producing adhesives, sole stock solution, adhesives and the like, and modified MDI used in the production of microporous elastomers, pouring elastomers, soft polyurethane foam plastics and the like is also the NCO-terminated prepolymer. In general, excess MDI reacts with difunctional polyols such as polyester polyol, polyether polyol and the like at a certain temperature for a certain time to obtain a prepolymer terminated by NCO groups. The prepolymer is used as a product to be filled into containers such as 20L or 200L iron barrels, IBC ton barrels and the like, and the quality guarantee period is generally 3-6 months under the room temperature condition. However, the industrial field often encounters the unstable abnormal phenomenon of the prepolymer product in the storage process, which is specifically shown as drum, greatly increased viscosity, turbid appearance, even solidification and the like.
The reason for the instability of the prepolymer is that the residual NCO groups are further reacted, and the side reactions comprise side reactions of generating dimers by self-polymerization of the NCO groups, producing urea and carbon dioxide gas by reaction of the NCO groups and water vapor, generating allophanate crosslinking structures by reaction of the NCO groups and carbamate and the like. The first two side reactions can be effectively inhibited and avoided by improving the storage conditions, for example, the generation rate of the dimer can be reduced to an acceptable range by controlling the storage temperature of the prepolymer to be 20-30 ℃; the nitrogen gas replacement can isolate the influence of steam when thoroughly drying and packing the container. However, the strict control of the external conditions has a limited effect of blocking the formation of allophanate crosslinked structures, and the formation of allophanates is more affected by catalytically active impurities in the prepolymer, such as residual titanate catalysts in polyester polyols (typically with a residual amount of 0.001 wt% to 0.01 wt%), residual potassium hydroxide catalysts in polyether polyols (typically with a residual amount of 0.0002 wt% to 0.005 wt%), and DMC bimetallic catalysts (typically with a residual amount of 0.001 wt% to 0.01 wt%), and iron components introduced during the production of the prepolymer (typically with a residual amount of 0.0001 wt% to 0.01 wt%). The impurities catalyze NCO groups to further react with carbamate to generate cross-linked allophanate, so that the viscosity of the prepolymer is greatly increased, and even the prepolymer product is cured.
The improvement of the storage stability of prepolymers can be achieved by reducing the catalyst residues in the polyols, and various measures have been tried in the prior art in the production of polyols, for example:
(1) the patent CN 101258181A discloses a method for reducing the catalyst usage amount in the polyether generation process, the surface of the invented solid acid catalyst contains hydroxyl which can combine with hydrophobic groups in reactants, thus improving the hydrophobicity of the catalyst and further slowing down the inactivation rate of the catalyst, thereby reducing the catalyst usage amount, ensuring lower catalyst residue in the product and reducing the impurity content.
(2) Patent CN 102911354a discloses a method for producing polyether polyol with low activity, which uses amine catalyst instead of traditional potassium hydroxide, and has relatively low catalytic activity and small influence on downstream even if remaining in polyether.
(3) Patent CN 106589345A describes a method for producing polyether with low VOC and odor, which is characterized in that magnesium silicate and aluminum silicate are added to be mixed as an adsorbent in the process of producing polyether, thereby removing part of catalyst and reducing the catalyst residue in the polyether product.
(4) Patent CN 111518268A adopts a method of adding inorganic acid such as phosphoric acid or sulfuric acid to reduce the activity of the residual bimetallic catalyst in the polyether, thereby reducing the influence of the polyether on the application of the prepolymer.
(5) In patent CN 108341941A, acid is one or more of phosphoric acid, sulfuric acid, hydrochloric acid, sulfurous acid, oxalic acid or acetic acid, which are mixed with pure water in a mass ratio of 1:5-12, and polyether is washed to remove catalyst.
The invention can realize the activity reduction of the polyol, is beneficial to improving the storage stability of the NCO group end-capping prepolymer and avoids the occurrence of allophanate crosslinking side reaction. However, in the method, the development cost of the new catalyst is high, the process is complex, and the cost advantage is difficult to form in the production of the polyol; the residual catalyst is removed by adopting an adsorbent or an acid washing and water washing mode, so that a large amount of solid waste and waste liquid can be generated. In addition, in any mode, the activity of the polyol is only reduced as much as possible, and the absolute storage stability of the prepared prepolymer cannot be guaranteed.
Disclosure of Invention
The invention provides a method for improving the storage stability of a prepolymer to make up for the defects in the prior art, and mainly solves the problem of poor storage stability of the prepolymer caused by high activity of polyol.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for improving the storage stability of a prepolymer by adding an effective amount of an additive to the system, the additive comprising a) a phosphate ester and b) a silane coupling agent.
Preferably, as component a) a phosphate ester, the structural formula of which is at least one of the formulae (I), (II), (III):
wherein R in the formula (I) 1 、R 2 Are each a hydrogen atom, a hydrocarbon group or an aryl group, R 1 And R 2 Which may be the same or different, R 1 And R 2 At least one of (a) is a hydrocarbyl group, preferably an alkyl group of C8-C18, or an aryl group, preferably phenyl, tolyl;
in the formulae (II) and (III), R 3 And R 4 Each is a hydrogen atom, a hydrocarbon group or an aryl group, R 3 And R 4 May be the same or differentIn a different sense, R 3 And R 4 At least one of them is a hydrocarbon group, preferably an alkyl group having C2-C6, or an aryl group, preferably a phenyl group or tolyl group, AO is an alkylene oxide group, preferably oxyethylene group or oxypropylene group, each AO may be the same or different, n represents an integer of 1 or more, preferably 1 to 10, and each n may be the same or different.
As component b) the silane coupling agent, at least one selected from the group consisting of KH550, KH792 and KH 602.
In the method of the present invention, the additive may be previously added to isocyanate (preferably MDI) or polyol, or may be added to the prepolymer after completion of the reaction for preparing the prepolymer, and as a preferable embodiment, the additive is previously added to isocyanate. a) The component is added in an amount of 0.0001 to 0.01 wt% of the mass of the isocyanate, the component b) is added in an amount of 0.0001 to 0.02 wt% of the mass of the isocyanate, and the addition amount is larger than that of the phosphate of a).
In the method of the present invention, as a preferable scheme, the additive is added into MDI in advance, in order to obtain good compatibility between the additive and the MDI, the component a) phosphate ester should be added into the MDI firstly, the adding amount is 0.0001-0.01 wt%, preferably 0.001-0.004 wt% of the mass of the MDI, after the phosphate ester and the MDI are mixed uniformly, the component b) silane coupling agent is added, the adding amount is 0.0001-0.02 wt%, preferably 0.002-0.010 wt% of the mass of the MDI, and the adding amount is more than that of the component a) phosphate ester. The MDI added with the additive of the invention basically has no abnormity such as viscosity rising and the like in the storage process of the synthesized prepolymer.
In the additive, the phosphate shows an excellent shielding effect on residual catalyst impurities in the polyol, namely, after the phosphate is added, the produced prepolymer has excellent storage stability and almost has no abnormal phenomena such as viscosity rise and the like. However, the phosphate ester is acidic, reactive with MDI and not stable in MDI; the silane coupling agent is alkaline and has the same reactivity with phosphate and MDI, when the three substances coexist, the phosphate can preferentially react with the silane coupling agent due to subtle difference of reaction rates of the three substances by reasonably controlling the amount of the two additives, and a product loses the reactivity with the MDI due to large steric hindrance and the like and can be uniformly distributed in the MDI; the reaction product of the phosphate ester and the silane coupling agent still has a shielding effect on residual catalyst impurities in the polyol.
The method for improving the applicability of the MDI in the prepolymer by adding the phosphate ester and the silane coupling agent into the MDI does not change the reactivity of the monomer isocyanate, and the obtained MDI can be widely applied to modified MDI used in the production of adhesives, sole stock solution, adhesives, microporous elastomers, pouring elastomers, soft polyurethane foam plastics and the like. As an example, the invention applies to the production of flexible packaging laminating adhesives: the molecular weight of the raw material polyoxypropylene ether glycol can be 1000-3000, the content of 2, 4' -diphenylmethane diisocyanate isomer in the raw material MDI can be 0.80-1.80 wt%, the NCO residual quantity of the prepolymer can be 1.0-20.0%, the reaction in the production process is stable, the process is easy to control, and the viscosity amplitude of the prepolymer obtained by reaction is less than 5% after the prepolymer is stored for 6 months at room temperature; this is merely an example and is not intended to be limiting.
The technical scheme provided by the invention has the following beneficial effects:
the additive can effectively avoid the allophanate crosslinking side reaction, thereby overcoming the viscosity rising, turbidity, solidification and other abnormalities of the prepolymer in the storage process and improving the quality of the prepolymer product. The method for improving the stability of the polyurethane prepolymer avoids the complex operations of adsorption, acid washing, water washing and the like and the generation of three wastes in the production of the polyol.
By adding phosphate ester and silane coupling agent in MDI in sequence, the prepolymer can stably exist in MDI, and can inhibit the influence of residual catalyst impurities in polyol in the application of the prepolymer, inhibit the occurrence of side reaction, improve the storage stability of the prepolymer, prolong the storage time and improve the value of the prepolymer product.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The following experimental procedures are, unless otherwise specified, all conventional procedures in the art, and the starting materials or reagents used therein are, unless otherwise specified, commercially available starting materials or reagents.
Wherein: MDI uses WANNATE MDI-100 of wanhua chemistry,
the polyether polyol is C2010B of Wanhua chemistry, wherein the residual catalyst is KOH, the residual amount is 5-20ppm,
the polyester polyol is PBA-2000 of Wanhua chemistry, the catalyst residue is titanate, and the residual amount is 10-50 ppm;
the mixer was chosen to be EURO STAR 2000D,
the temperature recorder adopts Hangzhou ancient automated CX6316R,
the viscometer is a BROOK FIELD.
The prepolymer is prepared by adopting an industry general method, and the required NCO residual quantity of the prepolymer is obtained by adjusting the using amounts of MDI and polyhydric alcohol.
The stability evaluation of the prepolymer adopts a high-temperature degradation mode, the prepolymer is placed in an oven at 80 ℃ for 24 hours, and the viscosity of the prepolymer before and after degradation is tested.
Example 1
a) Component phosphate selection
(octadecyl phosphate, seaan chemical);
b) the component is selected from KH-550(KBM-903, Japan shines).
a) The component b) and the component b) are added into MDI (phosphate ester addition amount is 0.004 percent of the MDI, the component b) addition amount is 0.008 percent), and prepolymer 1# with 16 percent of NCO residual amount is synthesized with C2010B. Simultaneously, a blank MDI experiment without additives is carried out to obtain prepolymer No. 2.
The viscosities of the two prepolymers before and after degradation were tested. The results are shown in the following table.
| Performed polymer | viscosity/mPas before deterioration | viscosity/mPas after deterioration |
| 1# | 218 | 228 |
| 2# | 224 | 36120 |
Therefore, the additive greatly improves the storage stability of the polyether prepolymer, and the viscosity rise after deterioration is only 4.6%.
Example 2
a) Component phosphate selection
(diisooctyl phosphate, alatin),
b) the component is selected from KH-602(A-2120, United states carbon).
Synthesizing a prepolymer with 16% of NCO residual quantity by MDI and PBA-2000, and adding the component a) and the component b) in sequence, wherein the addition amounts are 0.001% and 0.003% of the mass of MDI respectively, so as to obtain the prepolymer No. 3. And simultaneously carrying out a blank experiment without additives to obtain prepolymer No. 4.
The viscosities of the two prepolymers before and after degradation were tested. The results are shown in the following table.
| Performed polymer | viscosity/mPas before deterioration | viscosity/mPas after deterioration |
| 3# | 1513 | 1514 |
| 4# | 1520 | 1866 |
Therefore, the additive greatly improves the storage stability of the polyester prepolymer, and the viscosity is hardly increased after the deterioration.
Example 3
a) Selection of component phosphate
(butoxyethyl phosphate, Meclin),
b) the component is selected from KH792(Z-6020, Dow Corning USA).
Sequentially adding the component a) and the component b) into C2020B, wherein the addition amounts are 0.002% and 0.004% of the mass of MDI respectively, and reacting with MDI to prepare prepolymer 5# with 5% of NCO residual quantity. And simultaneously carrying out a blank experiment without additives to obtain prepolymer No. 6.
The viscosities of the two prepolymers before and after degradation were tested. The results are shown in the following table.
| Performed polymer | viscosity/mPa. before deteriorations | viscosity/mPas after deterioration |
| 5# | 3526 | 3544 |
| 6# | 3617 | 46375 |
The additive is added into polyether, so that the storage stability of the prepolymer is effectively improved, and the viscosity of the prepolymer is basically not increased after the prepolymer is degraded.
Example 4
a) Component phosphate selection
(bis propylene oxide ethyl phosphate, Yousol chemical);
b) the component is selected from KH-550(KBM-903, Japan shines).
a) The component a and the component b) are added into MDI (the adding amount of the component a is 0.007 percent of the MDI, the adding amount of the component b is 0.015 percent) in sequence, and prepolymer 7# with 5 percent of NCO residual amount is synthesized with PBA-2000. Simultaneously, a blank MDI experiment without additives is carried out to obtain a prepolymer No. 8.
The viscosities of the two prepolymers before and after degradation were tested. The results are shown in the following table.
| Performed polymer | viscosity/mPas before deterioration | viscosity/mPas after deterioration |
| 7# | 4469 | 4478 |
| 8# | 4574 | 20132 |
The additive is added into MDI, so that the storage stability of the prepolymer is greatly improved, and the viscosity of the prepolymer is basically not increased after the prepolymer is degraded.
Comparative example 1
a) Selection of component phosphate
(octadecyl phosphate, seaman chemical);
b) the component is selected from KH-550(KBM-903, Japan shines).
a) The component b) and the component b) are added into MDI (the adding amount of the phosphate is 0.004 percent of the MDI, the adding amount of the component b) is 0.001 percent), and synthesized with C2010B to obtain prepolymer 9# with 16 percent of NCO residual quantity. Simultaneously, a blank MDI experiment without additives is carried out to obtain prepolymer No. 10.
The viscosities of the two prepolymers before and after degradation were tested. The results are shown in the following table.
| Performed polymer | viscosity/mPas before deterioration | viscosity/mPas after deterioration |
| 9# | 221 | 15643 |
| 10# | 224 | 36120 |
When the addition amount of the component b) is less than that of the component a), the effect of improving the stability of the prepolymer is greatly reduced.
Claims (7)
1. The method for improving the storage stability of the polyurethane prepolymer is characterized in that an additive is added into a system, wherein the additive comprises a) phosphate and b) a silane coupling agent.
2. The method according to claim 1, wherein a) the phosphate ester is at least one selected from the group consisting of compounds represented by the following formulae (I), (II) and (III):
wherein, in the formula (I), R 1 、R 2 Identical or different, are each a hydrogen atom, a hydrocarbon group or an aryl group, R 1 And R 2 At least one of (a) is a hydrocarbyl group, preferably an alkyl group of C8-C18, or an aryl group, preferably phenyl, tolyl;
in the formulae (II) and (III), R 3 And R 4 Identical or different, are each a hydrogen atom, a hydrocarbon group or an aryl group, R 3 And R 4 At least one of them is a hydrocarbon group, preferably an alkyl group of C2-C6, or an aryl group, preferably a phenyl group or tolyl group, AO is an alkylene oxide group, preferably an oxyethylene group or an oxypropylene group, each AO is the same or different, n represents an integer of 1 or more, preferably 1-10, and each n is the same or different.
3. The method according to claim 1 or 2, wherein b) the silane coupling agent is at least one selected from the group consisting of KH550, KH792 and KH 602.
4. The method according to any one of claims 1 to 3, wherein a) the phosphate ester is added in an amount of 0.0001 to 0.01 wt%, b) the silane coupling agent is added in an amount of 0.0001 to 0.02 wt%, and b) the amount of b) is larger than that of a), based on the weight of the isocyanate for preparing the polyurethane prepolymer.
5. The process of any of claims 1-4, wherein the isocyanate used to prepare the polyurethane prepolymer is MDI.
6. The process according to claim 5, wherein the additive is pre-added to the MDI in the order a) phosphate ester, b) silane coupling agent.
7. A polyurethane prepolymer obtained by the method according to any one of claims 1 to 6.
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