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CN111647346B - Prepolymer composition and barrier material - Google Patents

Prepolymer composition and barrier material Download PDF

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Publication number
CN111647346B
CN111647346B CN202010532730.1A CN202010532730A CN111647346B CN 111647346 B CN111647346 B CN 111647346B CN 202010532730 A CN202010532730 A CN 202010532730A CN 111647346 B CN111647346 B CN 111647346B
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prepolymer
parts
polyisocyanate
compound
composition
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CN111647346A (en
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马仁林
陈鹏
吴建忠
张会仙
师梁
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Shaanxi Yangling Panji New Material Technology Co ltd
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Shaanxi Yangling Panji New Material Technology Co ltd
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/08Polyurethanes from polyethers
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/70Additives characterised by shape, e.g. fibres, flakes or microspheres
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24Acids; Salts thereof
    • C08K3/26Carbonates; Bicarbonates
    • C08K2003/265Calcium, strontium or barium carbonate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The invention relates to the field of track slab insulating materials, in particular to a prepolymer composition and an insulating material. A prepolymer composition, comprising a prepolymer and a silane compound; the prepolymer comprises (a) a prepolymer I obtained by copolymerizing polyether polyol, phenolic resin or a mixture of the polyether polyol and the phenolic resin with polyisocyanate and (b) a prepolymer II obtained by copolymerizing polyester polyol, a compound of a general formula (I) or a mixture of the polyester polyol and the compound of the general formula (I) with polyisocyanate, wherein the prepolymer (a): (b) (30-40): (15-25). The prepolymer I and the prepolymer II are mixed according to a specific ratio, so that the high-low temperature stability and water resistance are achieved, the temperature resistance is substantially improved, cement with high hydration heat is prevented from swelling and cracking under the condition of excellent water resistance, and finally, the safety is greatly improved under the combined action of external factors and internal factors.

Description

Prepolymer composition and barrier material
Technical Field
The invention relates to the field of track slab insulating materials, in particular to a prepolymer composition and an insulating material.
Background
The isolation material is sprayed on the track slab at the position which can be contacted with cast-in-place concrete to form a material which is attached to the track slab and has a certain thickness. The main functions are as follows: (1) the cast-in-place concrete and the precast slabs are isolated, so that the track slab can be conveniently separated from the cast-in-place structure during hoisting when the track slab needs to be replaced after the track traffic is operated; (2) the limiting part of the track plate plays a certain role in buffering, so that the problem of stress concentration of the track plate at the limiting structure is avoided; (3) the isolation material also has good waterproof and insulating properties, is favorable for preventing the surface of the track slab from seeping water and protecting stray current, and improves the durability of the track slab.
However, the cracking of the track slab is one of the important technical problems in the construction and operation of the high-speed railway, and once the crack is formed, the crack causes great harm, which reduces the durability of the track, reduces the insulating performance of the track, weakens the bearing capacity of the track, and may also cause adverse effects on the use safety of the track. Because the high-performance concrete has large cement consumption and high hydration heat, the internal temperature of the concrete rises and the concrete expands; the concrete external temperature will decrease due to the non-adiabatic state of the element. When the tensile stress produced by the shrinkage of the concrete exceeds the tensile strength of the concrete, the concrete will crack.
At present, the rail plate cracks caused by temperature are not effectively solved, a later-stage repairing technology is mostly adopted, a repairing material is usually high-permeability organic resin, the material can effectively delay reinforcing steel bar corrosion and concrete carbonization caused by the cracks, and the problems cannot be fundamentally solved.
Disclosure of Invention
Unless otherwise indicated, implied from the context, or customary in the art, all parts and percentages herein are by weight and the testing and characterization methods used are synchronized with the filing date of the present application. To the extent that a definition of a particular term disclosed in the prior art is inconsistent with any definitions provided herein, the definition of the term provided herein controls.
The words "preferred", "preferably", "more preferred", and the like, in the present invention, refer to embodiments of the invention that may provide certain benefits, under certain circumstances. However, other embodiments may be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention. The sources of components not mentioned in the present invention are all commercially available.
After earnest study to solve the above problems, the present inventors have found that by mixing prepolymer i and prepolymer ii described below at a specific ratio, excellent high/low temperature stability and water resistance can be obtained, and this not only substantially improves the temperature resistance, but also prevents cement expansion cracking due to high heat of hydration due to excellent water resistance, and finally greatly improves the safety due to the combined action of external factors and internal factors.
The invention provides a prepolymer composition in a first aspect, which comprises a prepolymer and a silane compound; the prepolymer comprises (a) a prepolymer I obtained by copolymerizing polyether polyol, phenolic resin or a mixture of the polyether polyol and the phenolic resin with polyisocyanate and (b) a prepolymer II obtained by copolymerizing polyester polyol, a compound of the general formula (I) or a mixture of the polyester polyol and the compound of the general formula (I) with polyisocyanate, wherein the prepolymer (a): (b) (30-40): (15-25); more preferably (33 to 38): (18-23).
(a) Prepolymer I
In a preferred embodiment of the present invention, the component (a) is a prepolymer I obtained by copolymerizing a polyether polyol, a phenol resin, or a mixture thereof with a polyisocyanate.
In some embodiments of the present invention, the polyether polyol is selected from at least one of polyoxypropylene diol, polyoxypropylene triol, polyoxypropylene tetraol, polytetrahydrofuran diol; preferably, the polyether polyol with the weight average molecular weight of 1000-8000 is selected as the monomer of the polyether polyol, more preferably, the polyether polyol has the weight average molecular weight of 2000-6000, and the polyether polyol with the molecular weight of more than 8000 is easy to cause excessive reaction viscosity and is not beneficial to production, so the adding amount of the polyether polyol is suitable, usually 50-80 wt%, preferably 60-75 wt% in the total reaction materials; most preferably, the present invention employs two or more polyether polyols for copolymerization.
The weight average molecular weight herein refers to the molecular weight as a statistical average of molecular weights. Usually expressed as Mw, which is equal to the sum of the molecular weight of each molecule multiplied by its weight fraction.
In a preferred embodiment of the present invention, the phenol resin includes, for example, an alkyl phenol resin, a terpene phenol resin, a hydrogenated terpene phenol resin, a rosin-modified phenol resin, and the like.
(b) Prepolymer II
In a preferred embodiment of the present invention, the component (b) is a prepolymer II obtained by copolymerizing a polyester polyol, a compound of the formula (I), or a mixture thereof with a polyisocyanate.
In some embodiments of the present invention, the polyester polyol is specifically exemplified by: polyester polyols obtained by subjecting aromatic carboxylic acids such as terephthalic acid and isophthalic acid, acid esters thereof, acid anhydrides thereof, and the like to dehydration condensation with polyhydric alcohols; or polyester polyols obtained by subjecting the above aromatic carboxylic acids, acid esters, acid anhydrides thereof, and other aromatic carboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid, acid esters, acid anhydrides thereof, and the like, and polyhydric alcohols to dehydration condensation; or a mixture of a polyester polyol obtained by subjecting a polyhydric alcohol and the above aromatic carboxylic acid, acid ester thereof, acid anhydride thereof, or the like to dehydration condensation with another polyester polyol; or polyester polyols obtained by dehydration condensation reaction of aromatic or non-aromatic carboxylic acids such as succinic acid, adipic acid, sebacic acid, azelaic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid, acid esters and acid anhydrides thereof, and polyhydric alcohols. Examples of the polyol include: diols and triols such as ethylene glycol, 1, 3-propanediol, 1, 2-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 3-methyl-1, 5-pentanediol, 2-butyl-2-ethyl-1, 3-propanediol, neopentyl glycol, 1, 8-octanediol, 1, 9-nonanediol, diethylene glycol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, dimer acid diol, trimethylolpropane, glycerol, hexanetriol, or an adduct of ethylene oxide or propylene oxide thereof. These polyester polyols may be used alone, or two or more kinds of polyols may be used in combination. Among them, polyester polyols having a hydroxyl value of 40 to 300 are preferred, and examples of the polyester polyols include, but are not limited to, polyethylene adipate.
In a preferred embodiment of the present invention, the compound of formula (i) is:
Figure BDA0002535934280000031
wherein R1, R2, R3, R4, R5 and R6 respectively and independently represent a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C2-C12 alkenyl group and a substituted or unsubstituted C1-C12 alkaneOxy, substituted or unsubstituted C1-C8 acyl, substituted or unsubstituted aryl, cyano, hydroxyl, amino, carboxyl, mercapto, sulfonic acid, nitro, amide, alkynyl, azo.
In a preferred embodiment of the present invention, the C1-C12 alkyl group and the substituted C1-C12 alkyl group include, but are not limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2- (2-methyl) butyl, 2- (2, 3-dimethyl) butyl, 2- (2-methyl) pentyl, neopentyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, cyclopentyl, hydroxycyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexyl, cyclohexylmethyl, hydroxycyclohexyl, benzyl, phenethyl, naphthylmethyl, tetrahydronaphthyl and tetrahydronaphthylmethyl.
In a preferred embodiment of the present invention, the alkenyl group of C2-C12 includes, but is not limited to, allyl, styryl, cyclopentenyl, cyclopentenylmethyl, cyclopentenylethyl, cyclohexenyl, cyclohexenylmethyl, and indenyl.
In a preferred embodiment of the present invention, the C1-C12 alkoxy group and the substituted C1-C12 alkoxy group include, but are not limited to, methoxy, ethoxy, propoxy, butoxy, octyloxy, decyloxy, and the like.
In a more preferred embodiment of the present invention, R1, R2, R3, R4, R5 and R6 each independently represent a hydrogen atom, a substituted or unsubstituted C1-C8 alkyl group, a substituted or unsubstituted C2-C6 alkenyl group, a substituted or unsubstituted C1-C4 alkoxy group, or a substituted or unsubstituted C1-C4 acyl group.
In a more preferred embodiment of the present invention, said R1 and R2 each independently represent a substituted or unsubstituted C1-C8 alkyl group; r3 and R4 each independently represent a hydrogen atom, a substituted or unsubstituted C1-C8 alkyl group; r5 and R6 are the same and represent substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C2-C6 alkenyl, substituted or unsubstituted C1-C4 alkoxy and substituted or unsubstituted C1-C4 acyl. Particularly preferred compounds of the formula (I) include 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate, neopentyl glycol bisacetoacetate, neopentyl glycol diacrylate, neopentyl glycol bis (ethylhexanoate).
After research on the compound of the general formula (I), the compound is shown to be substituted or unsubstituted C1-C8 alkyl on R1 and R2, and corresponding ester groups are respectively substituted by the same substituent groups, for example, from the research of experiments 1 and 5, the performance of the isolation material is excellent, so that a polar chain segment contained in the process of preparing the prepolymer II by the special structure has stronger hydrogen bonding capability and permeability, the phenomenon that aromatic sheets of the prepolymer are stacked to form aggregates is avoided, the reaction viscosity is effectively reduced, and the orderliness of macromolecules is improved.
In some embodiments of the present invention, the polyisocyanate is selected from one or more of C8-26 aromatic diisocyanates, C4-22 chain aliphatic diisocyanates, C8-18 alicyclic diisocyanates, C10-18 aromatic aliphatic diisocyanates, and modified products of these diisocyanates.
Specific examples of the aromatic diisocyanate having C8 to 26 include 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, 2, 4-tolylene diisocyanate, 2, 6-tolylene diisocyanate, 2,4 ' -diphenylmethane diisocyanate, 4 ' -diphenylmethane diisocyanate (hereinafter abbreviated as MDI), 4 ' -diisocyanatobiphenyl, 3 ' -dimethyl-4, 4 ' -diisocyanatodiphenylmethane and 1, 5-naphthylene diisocyanate.
Specific examples of the chain aliphatic diisocyanate having C4 to C22 include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2, 4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2, 6-diisocyanatomethylhexanoate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2, 6-diisocyanatohexanoate and the like.
Specific examples of the C8-18 alicyclic diisocyanate include isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexyl-1, 2-dicarboxylate, 2, 5-norbornane diisocyanate, 2, 6-norbornane diisocyanate, and the like.
Specific examples of the C10-18 araliphatic diisocyanates include m-xylylene diisocyanate, p-xylylene diisocyanate, and α, α, α ', α' -tetramethylxylylene diisocyanate.
In a more preferred embodiment of the present invention, the aromatic diisocyanate having 8-26 carbon atoms is more preferred from the viewpoint of prepolymer reaction conditions and product characteristics; specifically, MDI or TDI is preferred.
In the study, by comparing the amounts of prepolymer I and prepolymer II, it was found that when the amount of prepolymer I was adjusted, the high temperature resistance and low temperature resistance were substantially unchanged, while the water soak resistance and water impermeability were significantly reduced, which was caused by the decrease in the crosslink density and/or the increase in the number of defects in the polymer chain due to the presence of prepolymer I alone. The comparison shows that the prepolymer I obtained by the reaction of the raw materials in the prepolymer I and the polyisocyanate has enough time and complete reaction, and then the prepolymer I and the prepolymer II react, so that the ordered regular arrangement of macromolecules is easily formed, and the water immersion resistance and water impermeability of the prepolymer I and the prepolymer II can be improved together.
When the content of the prepolymer II relative to the prepolymer I is very high and exceeds the preferable range (33-38): (18 to 23), the viscosity may be high, and cracks may be caused by self-thermal degradation after a test at a high temperature, and the thermal degradation phenomenon may be accelerated by the powder filler. Too small a content can also result in unstable water resistance of the isolating material; therefore, within a reasonable range, after cross-linking polymerization, the hard chain segment and the soft chain segment are most easily arranged in order, in fact, the difficulty that the stable and ordered arrangement of the chain segments can be controlled only by reducing the viscosity of the system under the premise of ensuring a certain solid content is generally solved in that the adjustment and control are needed under the conditions of a large amount of polyhydric alcohol and less isocyanate, but the adjustment and control of the proportion of the polyhydric alcohol and the isocyanate in the prior art obviously influence the high-temperature and low-temperature performance, and experiments prove that the lower viscosity can be ensured and the larger interaction and the better microphase separation degree among the macromolecules of the prepolymer can be promoted after the compound of the general formula (1) is considered.
Silane compound
In a more preferred embodiment of the invention, the silane compound contains at least one hydrolysable silane group. Hydrolyzable silyl groups having the formula-Si- (O-R)xStructure wherein x is 1 to 3, preferably 2 or 3, and R is hydrocarbyl or substituted hydrocarbyl. R may be, for example, lower alkyl (methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, etc.), cycloalkyl or alkyl-substituted cycloalkyl such as cyclohexyl, aryl-substituted alkyl such as benzyl, or phenyl or alkyl-substituted phenyl.
It is to be understood that the silane compound containing at least one hydrolyzable silane group includes derivatives thereof without affecting the hydrolyzable silane group thereof, and for example, such derivatives may be silane compounds containing at least one hydrolyzable silane group having an amino group, monoalkylamino group, isocyanate group, thioisocyanate group or alkenyl group.
In a more preferred embodiment of the present invention, the silane compound may specifically be exemplified by: silane compounds obtained by condensing mercaptoalkoxysilanes such as gamma-mercaptopropyltriethoxysilane, gamma-mercaptopropyltrimethoxysilane, and N atom-containing compounds such as dimethylpiperazine and the like.
The invention provides a second aspect of the isolation material, which comprises a prepolymer and a silane compound; the prepolymer comprises (a) a prepolymer I obtained by copolymerizing polyether polyol, phenolic resin or a mixture of the polyether polyol and the phenolic resin with polyisocyanate and (b) a prepolymer II obtained by copolymerizing polyester polyol, a compound of a general formula (I) or a mixture of the polyester polyol and the compound of the general formula (I) with polyisocyanate, wherein the mass ratio of the prepolymers (a) to the prepolymers (b) is (a): (b) (35-36): (20-21). Generally, the amount of the added prepolymer is 40-95 wt%, preferably 50-90 wt%, based on the total weight of the isolation material; the amount of the silane compound added is 1 to 10 wt%, preferably 2 to 5 wt%.
In a more preferred embodiment of the invention, the barrier material further comprises a tackifier, a compatibilizer, and a powder filler.
As a tackifier for a barrier material, in order to improve adhesion characteristics, a tackifier suitable for the present invention is preferably a monomer, a polymer and a derivative of ethylene-vinyl acetate, or a monomer, a polymer and a derivative of a hydrocarbon resin having 5 to 9 carbon atoms, or a monomer, a copolymer and a derivative of a C5/C9 hydrocarbon resin, specifically, a terpene tackifier, and is usually added in an amount of 5 to 20 wt%, preferably 7.07 to 13.68 wt%, based on the total mass of the barrier material.
As the compatibilizing agent for the release material, for example, silane coupling agents, polyethylene wax, polypropylene wax, and polytetrafluoroethylene, tin-based compounds, and the like can be cited, and preferred silane coupling agents include, but are not limited to: amino silane coupling agent, mercapto silane coupling agent, epoxy silane coupling agent and alkyl silane coupling agent; preferred tin-based compounds include, but are not limited to, butyltin dilaurate, dibutyltin dichloride, dibutyltin diacetate, stannous octoate, dibutyltin dilaurate, tin tetrafluoride, tin tetrachloride, tin tetrabromide, tin tetraiodide, tin methyltrichloride, butyltin trichloride, dimethyltin dichloride, dibutyltin dichloride, trimethyltin chloride, tributyltin chloride, triphenyltin chloride, dibutyltin sulfide, bis (2-ethylhexyl) tin oxide, and the like. Suitable compatibilizers for use in the present invention include silane coupling agents, polyethylene waxes, polypropylene waxes, and combinations of any two of polytetrafluoroethylene and tin-based compounds; specifically, KH560 and dibutyltin dilaurate are preferable; the addition amount of the compatilizer is usually 0.1-1 wt% of the total mass of the isolation material.
Examples of the powder filler used for the separator include an organic powder filler and an inorganic powder filler. Examples of the organic powder filler include at least one selected from cellulose powders such as wood powder and pulp powder, polymer beads, and polymer hollow particles. For example, the inorganic powder filler may be at least one selected from the group consisting of: calcium carbonate, magnesium carbonate, barium carbonate, magnesium sulfate, barium sulfate, calcium sulfate, zinc oxide, magnesium oxide, calcium oxide, titanium oxide, aluminum hydroxide, hydroxyapatite, silica, white carbon, mica, talc, kaolin, clay, glass powder, asbestos powder, zeolite, terra alba, and the like. Among them, a mixture of 1 or 2 or more selected from calcium carbonate, white carbon, zinc oxide, barium sulfate, and titanium oxide is preferable. The amount of such a filler is usually 10 to 50 wt%, preferably 20 to 30 wt%, based on the total mass of the separator.
Further, the composition may further contain an antioxidant, a light stabilizer, a heat stabilizer, a dispersant, an ultraviolet absorber, a fluorescent brightener, and other additives within a range not to impair the above effects.
Detailed Description
The present invention is described in detail below with reference to examples, which are provided for the purpose of further illustration only and are not to be construed as limiting the scope of the present invention, and the insubstantial modifications and adaptations thereof by those skilled in the art based on the teachings of the present invention will still fall within the scope of the present invention.
Unless otherwise indicated, the terpene tackifiers of the examples are all trimodal brands of terpene resins from zhengzhou sky chemical products ltd.
Example 1
The special spraying isolation material raw materials for the railway track slab: 33 parts of prepolymer I, 23 parts of prepolymer II, 2.5 parts of silane compound, 9.13 parts of terpene tackifier, 24.5 parts of light calcium powder (1250 meshes), 7.5 parts of white carbon black, KH 5600.35 parts, dibutyltin dilaurate: 0.02 part.
The manufacturing process of the special spraying isolation material for the railway track slab comprises the following steps: keeping the light calcium powder and the white carbon black at 105 ℃ for 24 hours, and drying for later use; adding the prepolymer I, the prepolymer II, the silane compound and the terpene tackifier synthesized in the steps into a reaction kettle in proportion, stirring, adding powder when heating to about 60 ℃, uniformly stirring, starting a vacuum pump to slowly raise the vacuum degree to 0.095-0.1 (gauge pressure negative pressure), raising the temperature to 100-105 ℃, keeping the temperature for about 3.5 hours, and cooling to 80 ℃; adding KH-560, stirring, and cooling to 40 deg.C; adding dibutyltin dilaurate, stirring for 20min, discharging, and packaging under the protection of nitrogen to obtain the final isolation material.
Prepolymer I
Raw materials: parts by mass (100 in total), polyoxypropylene glycol (molecular weight 2000): 50.0 parts of polyoxypropylene triol (molecular weight is 6000): 22.0 parts of MDI: 17.0 parts of hydrogenated terpene phenolic resin: 6.0 parts of (B); adding the polyoxypropylene diol, the polyoxypropylene triol and the hydrogenated terpene phenolic resin in parts by weight into a reaction kettle, starting a stirrer, heating to about 60 ℃, starting a vacuum pump, slowly raising the vacuum degree to 0.095-0.1 (gauge pressure negative pressure), raising the temperature to 110-120 ℃, keeping for about 4 hours, cooling to 80 ℃, dripping MDI (diphenyl methane diisocyanate), stirring under vacuum for 5 hours, discharging, and placing in a sealed container under the protection of nitrogen for later use.
Prepolymer II
Raw materials: parts by mass (total 100), polyethylene adipate diethylene glycol ester: 56 parts of 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate: 15 parts of TDI: 20 parts of butanone oxime: 9 parts of (1); adding the polyethylene glycol adipate, the 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate and the TDI into a reaction kettle in parts by weight, starting a vacuum pump, slowly raising the vacuum degree to 0.095-0.1 (gauge pressure negative pressure), raising the temperature to 100-105 ℃, keeping the temperature for about 2 hours, adding the butanone oxime, stirring and reacting for 5 hours under vacuum, discharging, and placing in a sealed container for later use under the protection of nitrogen.
Silane compound
Raw materials: HDI biuret: 78.9 parts of gamma-mercaptopropyltrimethylsilane: 20.9 parts of dimethyl piperazine: 0.06 part. Adding the HDI biuret and the gamma-mercaptopropyl trimethylsilane in parts by weight into a reaction kettle, starting a vacuum pump, slowly increasing the vacuum degree to 0.095-0.1 (gauge pressure negative pressure), heating to 100-105 ℃, keeping for about 2.5h, cooling to 80 ℃, adding the dimethylpiperazine, stirring in vacuum for 30min, discharging, and storing for later use under the protection of nitrogen.
The performance tests of the insulation of example 1 are shown in table 1 below:
TABLE 1 technical indices of the insulation materials
Figure BDA0002535934280000081
Figure BDA0002535934280000091
Example 2
The special spraying isolation material raw materials for the railway track slab: 38 parts of prepolymer I, 18 parts of prepolymer II, 2.5 parts of silane compound, 9.13 parts of terpene tackifier, 24.5 parts of light calcium powder (1250 meshes), 7.5 parts of white carbon black, KH 5600.35 parts, dibutyltin dilaurate: 0.02 part.
Prepolymer I, prepolymer II and silane compound were prepared as in example 1, and the preparation process was the same as in example 1.
Example 3
The special spraying isolation material raw materials for the railway track slab: 15 parts of prepolymer I, 41 parts of prepolymer II, 2.5 parts of silane compound, 9.13 parts of terpene tackifier, 24.5 parts of light calcium powder (1250 meshes), 7.5 parts of white carbon black, KH 5600.35 parts, dibutyltin dilaurate: 0.02 part.
Prepolymer I, prepolymer II and silane compound were prepared as in example 1, and the preparation process was the same as in example 1.
Example 4
The special spraying isolation material raw materials for the railway track slab: 50 parts of prepolymer I, 6 parts of prepolymer II, 2.5 parts of silane compound, 9.13 parts of terpene tackifier, 24.5 parts of light calcium powder (1250 meshes), 7.5 parts of white carbon black, KH 5600.35 parts of dibutyltin dilaurate: 0.02 part.
Prepolymer I, prepolymer II and silane compound were prepared as in example 1, and the preparation process was the same as in example 1.
Example 5
The special spraying isolation material raw materials for the railway track slab: 33 parts of prepolymer I, 23 parts of prepolymer II, 2.5 parts of silane compound, 9.13 parts of terpene tackifier, 24.5 parts of light calcium powder (1250 meshes), 7.5 parts of white carbon black, KH 5600.35 parts, dibutyltin dilaurate: 0.02 part.
Prepolymer I and silane compound were prepared as in example 1, except that 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate was replaced with neopentyl glycol bis (ethylhexanoate) in prepolymer II, as in example 1.
Example 6
The special spraying isolation material raw materials for the railway track slab: 33 parts of prepolymer I, 23 parts of prepolymer II, 2.5 parts of silane compound, 9.13 parts of terpene tackifier, 24.5 parts of light calcium powder (1250 meshes), 7.5 parts of white carbon black, KH 5600.35 parts, dibutyltin dilaurate: 0.02 part.
The preparation process of the prepolymer I, the prepolymer II and the silane compound is the same as that of example 1, except that 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate in the prepolymer II is replaced by trimethylolpropane trioleate.
Example 7
The special spraying isolation material raw materials for the railway track slab: 56 parts of prepolymer I, 2.5 parts of silane compound, 9.13 parts of terpene tackifier, 24.5 parts of light calcium powder (1250 meshes), 7.5 parts of white carbon black, KH 5600.35 parts, dibutyltin dilaurate: 0.02 part.
Prepolymer I, prepolymer II and silane compound were prepared as in example 1, and the preparation process was the same as in example 1.
Example 8
The special spraying isolation material raw materials for the railway track slab: 33 parts of prepolymer I, 23 parts of prepolymer II, 2.5 parts of silane compound, 9.13 parts of terpene tackifier, 24.5 parts of light calcium powder (1250 meshes), 7.5 parts of white carbon black, KH 5600.35 parts, dibutyltin dilaurate: 0.02 part.
The preparation process of the prepolymer I, the prepolymer II and the silane compound is the same as that of example 1, and the difference is that the prepolymer II comprises the following raw materials: parts by mass (100 in total), polyethylene adipate diglycol ester: 71 parts of TDI: 20 parts of butanone oxime: 9 parts (not including 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate).
Evaluation of Properties
1. High temperature resistance: referring to method A1.1 of 'test method of waterproof building coiled material, part 11 of asphalt waterproof coiled material heat resistance', a cured isolation material sample with the thickness of 2mm is placed in an oven and heated for 8 hours without flowing, sliding and dripping phenomena. .
2. Low temperature resistance: referring to 'asphalt waterproof coiled material low-temperature flexibility test' GB/T328.14-2007, the cured isolation material sample with the thickness of 2mm is placed in a freezer at the temperature of-70 ℃ and is free of cracks and breakage after being placed for 8 hours.
3. Water soaking resistance: the cured isolation material sample with the thickness of 2mm and the thickness of 100mm multiplied by 100mm is soaked in purified water, after being placed for 100 days, the isolation material sample does not swell or dissolve visually, and after being dried in the air, the isolation material sample is weighed to have the same quality as that before being soaked.
4. Water impermeability: the prepared isolation material in each example is prepared into a sample with the thickness of 2mm, and after the sample is solidified and is tested for 28 days according to the test method in GB328.10-2007 test method for waterproof coiled material for building asphalt and polymer coiled material impermeability, the result is 0.3MPa and 100d, and the waterproof performance is realized.
The results are shown in Table 1, and the results are rated using +, ++, +++ with more + indicating better results.
TABLE 2 evaluation table for performance of isolation material
Examples High temperature resistance Low temperature resistance Water immersion resistance Water impermeability
2 +++ +++ +++ +++
3 ++ +++ +++ +++
4 +++ +++ + ++
5 +++ +++ +++ +++
6 ++ +++ +++ +++
7 +++ +++ + +
8 + ++ +++ +++

Claims (8)

1. A prepolymer composition is characterized by comprising a prepolymer and a silane compound; the prepolymer comprises (a) a prepolymer I obtained by copolymerizing polyether polyol, phenolic resin and polyisocyanate and (b) a prepolymer II obtained by copolymerizing polyester polyol, a compound of a general formula (I) and polyisocyanate, wherein the mass ratio of the prepolymers (a) to (b) is (a): (b) = 33 to 38: (18-23);
the compounds of the general formula (I) include 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate, neopentyl glycol diacetoacetate, neopentyl glycol diacrylate, neopentyl glycol bis (ethylhexanoate).
2. The composition of claim 1, wherein the polyether polyol is selected from at least one of polyoxypropylene diol, polyoxypropylene triol, polyoxypropylene tetraol, and polytetrahydrofuran diol.
3. The composition of claim 2, wherein the polyether polyol has a weight average molecular weight of 1000 to 8000.
4. The composition of any one of claims 1 to 3, wherein the polyester polyol has a hydroxyl number of 40 to 300.
5. The composition according to claim 4, wherein the polyisocyanate is one or more selected from the group consisting of C8-26 aromatic diisocyanates, C4-22 chain aliphatic diisocyanates, C8-18 alicyclic diisocyanates, and modified products of these diisocyanates.
6. The composition of claim 5, wherein the silane compound contains at least one hydrolyzable silane group.
7. The isolating material is characterized by comprising a prepolymer and a silane compound; the prepolymer comprises (a) a prepolymer I obtained by copolymerizing polyether polyol, phenolic resin and polyisocyanate and (b) a prepolymer II obtained by copolymerizing polyester polyol, a compound of a general formula (I) and polyisocyanate, wherein the mass ratio of the prepolymers (a) to (b) is (a): (b) = 33 to 38: (18-23); the compound of the general formula (I) comprises 2,2, 4-trimethyl-1, 3-pentanediol diisobutyrate, neopentyl glycol diacetyl acetate, neopentyl glycol diacrylate and neopentyl glycol bis (ethyl hexanoate).
8. The insulation material of claim 7, further comprising a tackifier, a compatibilizer, and a powder filler.
CN202010532730.1A 2020-06-12 2020-06-12 Prepolymer composition and barrier material Active CN111647346B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102070766A (en) * 2010-12-27 2011-05-25 沈阳化工大学 Method for preparing novel polyether-polyester polyurethane material
CN102718940A (en) * 2012-06-28 2012-10-10 广州高金技术产业集团有限公司 High-bonding-strength and high-temperature-resisting phenolic resin modified polyurethane adhesive and preparation method thereof
CN105419701A (en) * 2015-11-24 2016-03-23 苏州盖德精细材料有限公司 Environment-friendly phenolic resin adhesive and preparation method thereof
CN106811166A (en) * 2016-12-30 2017-06-09 东莞市科惠工业材料有限公司 A kind of new double-component joint trimming agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102070766A (en) * 2010-12-27 2011-05-25 沈阳化工大学 Method for preparing novel polyether-polyester polyurethane material
CN102718940A (en) * 2012-06-28 2012-10-10 广州高金技术产业集团有限公司 High-bonding-strength and high-temperature-resisting phenolic resin modified polyurethane adhesive and preparation method thereof
CN105419701A (en) * 2015-11-24 2016-03-23 苏州盖德精细材料有限公司 Environment-friendly phenolic resin adhesive and preparation method thereof
CN106811166A (en) * 2016-12-30 2017-06-09 东莞市科惠工业材料有限公司 A kind of new double-component joint trimming agent

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