CN107459617A - A kind of LNG ship grad enhancement heat-insulating material and its short process making method - Google Patents

A kind of LNG ship grad enhancement heat-insulating material and its short process making method Download PDF

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Publication number
CN107459617A
CN107459617A CN201710562862.7A CN201710562862A CN107459617A CN 107459617 A CN107459617 A CN 107459617A CN 201710562862 A CN201710562862 A CN 201710562862A CN 107459617 A CN107459617 A CN 107459617A
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insulating material
ppg
heat
fire retardant
lng ship
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张洪斌
孙小伟
蔡志祥
韦越
位元元
谢燕萍
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Shanghai Jiaotong University
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Shanghai Jiaotong University
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Priority to CN201710562862.7A priority Critical patent/CN107459617A/en
Priority to PCT/CN2017/107524 priority patent/WO2019010862A1/en
Publication of CN107459617A publication Critical patent/CN107459617A/en
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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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers

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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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)

Abstract

The invention discloses a kind of LNG ship grad enhancement heat-insulating material and its short process making method, heat-insulating material component includes PPG, polyisocyanates, foaming agent, foam stabiliser, tertiary amine catalyst, organic tin catalyst, bromide fire retardant, Sb system fire retardant and continuous Glass Fiber Mat, mass ratio 100：140~160：25~50：1.5~2：0.2：0.9~1：80~85：20~25：10~40, heat-insulating material density is 70~130kg/m3Limited oxygen index is more than 30%, preparation process includes the links such as drying, molding, moulded from foam, curing, the demoulding, epidermis cutting, it is existing because differences in expansion easily comes off from secondary screen-wall metal wall surfaces to solve the heat-insulating material of prior art preparation, is also easy to produce crackle greatly close to shrinkage stress at low temperature and the problem of the destructible insulating structures such as temperature difference thermal stress caused greatly in heat-insulating shield two sides is excessive.Preparation method of the present invention is near net shape production technique, has the characteristics of short flow, saving glass, cost is low, production is easy, integrated molding, product good combination property.

Description

A kind of LNG ship grad enhancement heat-insulating material and its short process making method
Technical field
The present invention relates to heat-insulating material and preparation method thereof, and in particular to a kind of LNG carrier Type B cargo tank Grad enhancement heat-insulating material and its short process making method, belong to heat-insulating material preparing technical field.
Background technology
Liquefied natural gas (LNG) is that main component is cooled into about -163 DEG C of super-low liquid for the natural gas of methane. Storage and transportation space and cost can be greatlyd save after natural gas liquefaction.Due to the nitrogen oxides and sulfur dioxide that are discharged when LNG burns It is less, therefore it is acknowledged as a kind of clean energy resource.LNG ship is the main conveyance of liquefied natural gas, and wherein cargo tank is gone along with sb. to guard him The heat-insulating property and security of system are one of whether qualified important indicators of LNG ship.Because LNG ship cargo tank is in running Middle temperature alternating scope is big (temperature difference is up to more than 200 DEG C), if cargo tank heat-insulating property and security are bad, can cause LNG compared with High evaporation rate, it can also make pressure rise in cabin, danger to surface navigation safety.Therefore, need that high performance thermal insulation is installed in cargo tank Material.
Hard polyurethane foams (PUR) are widely used in the adiabatic system of LNG ship because its thermal conductivity factor is low.But due to close Spend low, PUR fracture strength is relatively low, and common PUR lower temperature resistances are also poor, standard GB/T 50264《Industrial equipment and pipeline are exhausted Hot engineering design code》It is middle that PUR is recommended into limit temperature as -65~80 DEG C.Therefore, ultralow temperature rings of the PUR at -163 DEG C It can be destroyed under border because of low fracture toughness and low-temperature stability.In addition, PUR for LNG ship under arms during meeting Produce larger thermal stress, the amplitude for depending mainly on the size of material coefficient of thermal expansion difference and temperature change of thermal stress.When PUR is used for During LNG ship cargo tank adiabatic system, the shrinkage stress at tank body low temperature is big, by LNG rock impact influenceed it is also big (Kim M H,Lee S M,Lee J M,et al.Fatigue strength assessment of MARK-III type LNG cargo containment system.Ocean Engineering,2010,37(14):1243-1252；Chun M S,Kim M H,Kim W S,et al.Experimental investigation on the impact behavior of membrane-type LNG carrier insulation system.Journal of Loss Prevention in the Process Industries,2009,22(6):901-907), it thus may be susceptible to cracked, cause heat insulation effect greatly Reduce；Meanwhile when PUR local environments temperature is arrived between room temperature or higher temperature for -163 DEG C, due to PUR high thermal insulation Make PUR plates both sides temperature different, board memory is in the big thermograde of the temperature difference so that big thermal stress to be produced inside PUR, in temperature Circulation and ship are easily damaged when rocking；Additionally, due to which PUR linear expansion coefficients vary with temperature greatly, PUR plates two sides temperature is not Together, linear expansion coefficient is also different, and PUR can produce differential deformation, and this, which is also resulted in, produces larger thermal stress in foam.In addition, Because PUR is different from the thermal coefficient of expansion of time screen-wall metallic plate and adhesive, in temperature alternating, cargo tank heat insulating construction meeting Come off destruction because of differences in expansion.Above-mentioned phenomenon can cause adiabatic system to be damaged, and weaken its heat-insulating property, shorten service life. Therefore, how to solve the adiabatic system damage problem caused by heat-insulating material thermal stress is excessive with material thermal expansion coefficient difference is One of urgent problem to be solved at present.
Publication No. CN101120068B Chinese patent application disclose it is a kind of second gas barrier and heat-insulating shield it Between utilize heating cushion connection method.Although bonding that this method solves adhesive between second gas barrier and heat-insulating shield is strong Degree with temperature change greatly the problem of, but not consider PUR can be produced at low temperature larger shrinkage stress with The problem of PUR is with expansion coefficients of metal wire difference.Therefore, in order to prevent PUR plates shrink from cracking, the thermal insulation of PUR plates is deteriorated Performance, extend the service life of heat insulation layer, it is necessary to be improved to the PUR heat-insulating shields of prior art.Publication No. CN106516017A Chinese patent application discloses one kind using composite foam glass plate and PUR plates to prepare LNG ship with absolutely The adiabatic system building method of hot plate.The adiabatic composite plate can be avoided effectively caused by heat-insulating material expansion coefficient difference absolutely Thermosphere damages problem, and can reduce PUR plates thermal stress as caused by difference variation and change.But this method need to use adhesive will PUR plates are bonded in foam glass plate surface, and PUR plates still suffer from that shrinkage stress is big, and there may be split for long service at low temperature The problem of line.Other MULTILAYER COMPOSITE also make it that preparation technology is cumbersome so that insulation material can not be directly processed into using one-step method Type.
The addition of glass fibre can effectively strengthen the mechanical property of insulation material, so as to reduce the unfavorable shadow of thermal stress Ring.However, because glass fibre itself thermal conductivity factor is high, the addition of glass fibre can cause thermal insulation of materials hydraulic performance decline, material Thermal conductivity factor increase with the increase of glass fibre addition.FGM (Functionally Graded Materials), it is that must bear to be more than 2000 DEG C of high temperature to solve shuttle motor combustion chamber wall side at first, it is another New ideas material (Kieback B, Neubrand A, the Riedel that side is subjected to the problem of ultralow temperature liquid hydrogen cooling and proposed H.Processing techniques for functionally graded materials.Materials Science and Engineering:A,2003,362(1):81-106), refer in the preparation process of material, using advanced compound Technology, make the microcosmic aspect such as the structure and composition of material that continuous graded be presented along specific direction, so that material Also continuous graded is presented in same direction in macro property, to adapt to varying environment, realizes the non-equal of certain specific function The strong multifunctional novel shaped material of matter, Objective.The present invention is based on grad enhancement method, integrated machine-shaping PUR heat-insulating materials, While by adding glass fibre to realize that mechanical property strengthens purpose, glass fibre can be reduced to greatest extent and is added and is drawn The influence that the heat-insulating property risen declines and manufacturing cost rises.At present, there has been no carry out grad enhancement using composite glass fiber Method prepare heat-insulating material, to solve above-mentioned LNG ship Type B cargo tank PUR heat-insulating shields report of problems.
The content of the invention
In view of the drawbacks described above of prior art, the technical problems to be solved by the invention are to be directed to LNG ship adiabatic system Present in because heat-insulating material thermal stress is excessive and material thermal expansion coefficient difference caused by adiabatic system damage problem, there is provided A kind of grad enhancement heat-insulating material for LNG ship and preparation method thereof.It is characterized in that material has two kinds of gradient-structures, when Because the influence of gravity causes polyurethane foam density gradient to be present in a step foam process；Second, by adjusting foaming speed Degree so that formation of foam bottom glass fiber is more, the few gradient glass fiber content structure of top glass fiber.
To achieve the above object, prepared the invention provides a kind of LNG ship with grad enhancement heat-insulating material and its short route Method.Concrete technical scheme is as follows：
The invention discloses a kind of LNG ship grad enhancement heat-insulating material, component includes PPG, polyisocyanic acid Ester, foaming agent, foam stabiliser, catalyst, fire retardant and continuous Glass Fiber Mat.
Further, PPG and polyisocyanates mass ratio are 100：140~160.
Further, PPG and foaming agent mass ratio are 100：25~50.
Further, PPG and foam stabiliser mass ratio are 100：1.5~2.
Further, catalyst includes tertiary amine catalyst and organic tin catalyst, PPG are urged with tertiary amines Agent mass ratio is 100：0.2, PPG is 100 with organic tin catalyst quality ratio：0.9~1.
Further, fire retardant includes bromide fire retardant and Sb system fire retardant, PPG and bromide fire retardant quality Than for 100：80~85, PPG is 100 with Sb system fire retardant mass ratio：20~25.
Further, PPG and continuous Glass Fiber Mat mass ratio are 100：10~40.
Further, for PPG using sucrose as initiator, sucrose hydroxyl value is 480~500mgKOH/g.
Further, polyisocyanates is poly methylene poly phenyl poly isocyanate, polymethylene polyphenyl polyisocyanic acid Ester degree of functionality is that 2.6~3.1, NCO mass fractions are 30.0%~32.0%.
Further, foaming agent is HFC class foaming agents, preferably hydrogenates fluothane hydrocarbon (HFC) foaming agent 1,1,1,3,3- five Fluorine butane HFC-365mfc.
Further, foam stabiliser is the silicon class surfactant of the polyether-modified structure containing Si-C.
Further, bromide fire retardant is environmentally friendly TDE, and Sb system fire retardant is antimony oxide, Average grain diameter is 0.7 μm.
Further, infiltrated dose of glass fiber bundle surface and silane coupler have carried out surface in continuous Glass Fiber Mat It is modified.
Further, grad enhancement heat-insulating material density is 70~130kg/m3, limited oxygen index is more than 30%.
A kind of preparation method the invention also discloses LNG ship with grad enhancement heat-insulating material, comprises the following steps：
Step 1：PPG, fire-retardant powder and continuous Glass Fiber Mat are placed in 90 DEG C of bars in air dry oven 24h is dried under part, it is standby to be then cooled to room temperature.
Step 2：Standby continuous Glass Fiber Mat is uniformly put down after being cut into the shape of suitable mould after step 1 is handled Mold bottom is layered on, fire retardant includes bromide fire retardant and Sb system fire retardant, and PPG, bromide fire retardant, antimony system are fire-retardant The mass ratio of agent and continuous Glass Fiber Mat is 100：80~85：20~25：20~40.
Step 3：By foam stabiliser, tertiary amine catalyst, organic tin catalyst, bromide fire retardant, Sb system fire retardant It is added in PPG and mixes with foaming agent, stir, then add polyisocyanates, stir, then falls Enter and moulded from foam is carried out in mould, obtain pouring mold base, PPG, foam stabiliser, tertiary amine catalyst, organic tin Catalyst, bromide fire retardant, Sb system fire retardant, the mass ratio of foaming agent and polyisocyanates are 100：1.5~2：0.2：0.9~ 1：80~85：20~25：25~50：140~160.
Step 4：Mold base will be poured and be put into air dry oven, 24h is cured under 70 DEG C of Conditions Conditions.
Step 5：After curing terminates, it is stripped to pouring mold base, obtains foamed material, then, use high-speed cutting machine The epidermis of the foamed material is cut off, obtains LNG ship grad enhancement heat-insulating material, heat-insulating material density is 70~130kg/ m3, limited oxygen index is more than 30%.
Further, moulded from foam mould is stainless steel, and releasing agent is scribbled in die surface.
The present invention is nearly end form, short route process for producing, sectional dimension when preparing material, is ensureing performance Under the premise of, the final shape and size using material section have been approached as far as possible.Different warming plates are glued from by the way of compound The production technology that conjunction prepares composite insulation boards is compared, and near net shape production technique realizes one-step method and is directly molded preparation, integration Machine-shaping avoid the MULTILAYER COMPOSITE of warming plate, shorten the technological process of production, simplify process procedure, improve production Efficiency, by realizing short route continuous production, reduce material trimming amount and following process link as far as possible, reduce warming plate Probability caused by surface defect, has saved production cost.
Beneficial effects of the present invention：
1st, preparation method provided by the invention is near net shape production technique, has short flow, saving glass fibre, cost The characteristics of low, production simplicity, integrated molding, product good combination property.
2nd, compared with the heat-insulating material of existing LNG ship, the grad enhancement heat-insulating material enhancing of LNG ship provided by the invention Effect is good, excellent performance, can suppress material interface and the internal extension that there may be defect.
3rd, in adiabatic system temperature change, can avoid the occurrence of because differences in expansion causes heat insulation layer to come off the phenomenon of damage, The stability of adiabatic system is good, extends the service life of adiabatic system.
4th, while can guarantee that mechanics enhancing effect, due to simply high in the big position glass fiber content of material thermal stress Relatively low in the small position glass fiber content of thermal stress, glass dosage is greatly lowered, so that material integral heat insulation performance is by glass The influence of addition fall below it is minimum, decrease material prepare cost.
Design, concrete structure and the caused technique effect of the present invention are described further below with reference to accompanying drawing, with It is fully understood from the purpose of the present invention, feature and effect.
Brief description of the drawings
Fig. 1 is the schematic diagram of the adiabatic system of a preferred embodiment of the present invention；
Fig. 2 is that existing PUR destroys schematic diagram under heat stress；
Fig. 3 schematic diagrames under thermal stress effect for heat-insulating material prepared by a preferred embodiment of the present invention.
Embodiment
Below in conjunction with the accompanying drawings and the present invention is described in further detail in specific embodiment.It should be understood that embodiment is simply The present invention is illustrated, rather than limits the scope of invention in any form.
As shown in Figure 1-Figure 3, Fig. 1 is the schematic diagram of the adiabatic system of the preferred embodiment of the present invention, and Fig. 2 is existing PUR destroy schematic diagram under heat stress, Fig. 3 is that heat-insulating material prepared by a preferred embodiment of the present invention acts in thermal stress Lower schematic diagram.Wherein, 1 is main screen-wall, and 2 be stay bolt, and 3 be time screen-wall, and 4 be that continuous Glass Fiber Mat strengthens polyurethane foam Plate, 5 be continuous Glass Fiber Mat, and 6 be water blocking layer, and 7 be protective layer, and 8 be nut and seal washer, and 9 be prior art main screen wall, 10 be prior art stay bolt, and 11 be prior art time screen-wall, and 12 be the crackle occurred in prior art polyurethane foam, and 13 are Prior art polyurethane foam board, 14 be prior art water blocking layer, and 15 be prior art protective layer, 16 be prior art nut and Seal washer.
Embodiment 1：
From raw material：It is PPG, poly methylene poly phenyl poly isocyanate, tertiary amine catalyst, organotin catalyzed Agent, TDE, antimony oxide, foam stabiliser, HFC-365mfc, continuous Glass Fiber Mat 5.
From the mass ratio of raw material：100：150：0.2：0.9：84：21：1.5：40：10.
Step 1：By PPG, TDE powder, antimony oxide powder and continuous Glass Fiber Mat 5 It is placed in air dry oven under the conditions of 90 DEG C and dries 24h, it is standby is then cooled to room temperature.
Step 2：Standby continuous Glass Fiber Mat 5 is cut into after the shape of suitable mould uniformly after step 1 is handled It is laid in mold bottom.
Step 3：By foam stabiliser, tertiary amine catalyst, organic tin catalyst, TDE, three oxidations two Antimony and HFC-365mfc, which are added in PPG, to be mixed, and is stirred, and it is more to be then rapidly added polymethylene polyphenyl again Isocyanates, 30~50s is stirred, be subsequently poured into moulded from foam in the mould for having continuous Glass Fiber Mat 5 that tiles, obtain pouring mould Base.
Step 4：After moulded from foam reacts 20 minutes, mould is put into air dry oven under the conditions of 70 DEG C and cures 24h, Foamed material after the demoulding, then, the epidermis of the foamed material is cut off using high-speed cutting machine, obtain LNG ship grad enhancement Heat-insulating material.
Embodiment 2：
From raw material：It is PPG, poly methylene poly phenyl poly isocyanate, tertiary amine catalyst, organotin catalyzed Agent, TDE, antimony oxide, foam stabiliser, HFC-365mfc, continuous Glass Fiber Mat 5.
From the mass ratio of raw material：100：150：0.2：0.9：84：21：1.5：40：20.
Step 1：By PPG, TDE powder, antimony oxide powder and continuous Glass Fiber Mat 5 It is placed in air dry oven under the conditions of 90 DEG C and dries 24h, it is standby is then cooled to room temperature.
Step 2：Standby continuous Glass Fiber Mat 5 is cut into after the shape of suitable mould uniformly after step 1 is handled It is laid in mold bottom.
Step 3：By foam stabiliser, tertiary amine catalyst, organic tin catalyst, TDE, three oxidations two Antimony and HFC-365mfc, which are added in PPG, to be mixed, and is stirred, and it is more to be then rapidly added polymethylene polyphenyl again Isocyanates, 30~50s is stirred, be subsequently poured into moulded from foam in the mould for having continuous Glass Fiber Mat 5 that tiles, obtain pouring mould Base.
Step 4：After moulded from foam reacts 20 minutes, mould is put into air dry oven under the conditions of 70 DEG C and cures 24h, Foamed material after the demoulding, then, the epidermis of the foamed material is cut off using high-speed cutting machine, obtain LNG ship grad enhancement Heat-insulating material.
Embodiment 3：
From raw material：It is PPG, poly methylene poly phenyl poly isocyanate, tertiary amine catalyst, organotin catalyzed Agent, TDE, antimony oxide, foam stabiliser, HFC-365mfc, continuous Glass Fiber Mat 5.
From the mass ratio of raw material：100：150：0.2：0.9：84：21：1.5：45：40.
Step 1：By PPG, TDE powder, antimony oxide powder and continuous Glass Fiber Mat 5 It is placed in air dry oven under the conditions of 90 DEG C and dries 24h, it is standby is then cooled to room temperature.
Step 2：Standby continuous Glass Fiber Mat 5 is cut into after the shape of suitable mould uniformly after step 1 is handled It is laid in mold bottom.
Step 3：By foam stabiliser, tertiary amine catalyst, organic tin catalyst, TDE, three oxidations two Antimony and HFC-365mfc, which are added in PPG, to be mixed, and is stirred, and it is more to be then rapidly added polymethylene polyphenyl again Isocyanates, 30~50s is stirred, be subsequently poured into moulded from foam in the mould for having continuous Glass Fiber Mat 5 that tiles, obtain pouring mould Base.
Step 4：After moulded from foam reacts 20 minutes, mould is put into air dry oven under the conditions of 70 DEG C and cures 24h, Foamed material after the demoulding, then, the epidermis of the foamed material is cut off using high-speed cutting machine, obtain LNG ship grad enhancement Heat-insulating material.
Embodiment 4：
From raw material：It is PPG, poly methylene poly phenyl poly isocyanate, tertiary amine catalyst, organotin catalyzed Agent, TDE, antimony oxide, foam stabiliser, HFC-365mfc, continuous Glass Fiber Mat 5.
From the mass ratio of raw material：100：150：0.2：0.9：84：21：1.5：30：10.
Step 1：By PPG, TDE powder, antimony oxide powder and continuous Glass Fiber Mat 5 It is placed in air dry oven under the conditions of 90 DEG C and dries 24h, it is standby is then cooled to room temperature.
Step 2：Standby continuous Glass Fiber Mat 5 is cut into after the shape of suitable mould uniformly after step 1 is handled It is laid in mold bottom.
Step 3：By foam stabiliser, tertiary amine catalyst, organic tin catalyst, TDE, three oxidations two Antimony and HFC-365mfc, which are added in PPG, to be mixed, and is stirred, and it is more to be then rapidly added polymethylene polyphenyl again Isocyanates, 30~50s is stirred, be subsequently poured into moulded from foam in the mould for having continuous Glass Fiber Mat 5 that tiles, obtain pouring mould Base.
Step 4：After moulded from foam reacts 20 minutes, mould is put into air dry oven under the conditions of 70 DEG C and cures 24h, Foamed material after the demoulding, then, the epidermis of the foamed material is cut off using high-speed cutting machine, obtain LNG ship grad enhancement Heat-insulating material.
Embodiment 5：
From raw material：It is PPG, poly methylene poly phenyl poly isocyanate, tertiary amine catalyst, organotin catalyzed Agent, TDE, antimony oxide, foam stabiliser, HFC-365mfc, continuous Glass Fiber Mat 5.
From the mass ratio of raw material：100：150：0.2：0.9：84：21：1.5：25：20.
Step 1：By PPG, TDE powder, antimony oxide powder and continuous Glass Fiber Mat 5 It is placed in air dry oven under the conditions of 90 DEG C and dries 24h, it is standby is then cooled to room temperature.
Step 2：Standby continuous Glass Fiber Mat 5 is cut into after the shape of suitable mould uniformly after step 1 is handled It is laid in mold bottom.
Step 3：By foam stabiliser, tertiary amine catalyst, organic tin catalyst, TDE, three oxidations two Antimony and HFC-365mfc, which are added in PPG, to be mixed, and is stirred, and it is more to be then rapidly added polymethylene polyphenyl again Isocyanates, 30~50s is stirred, be subsequently poured into moulded from foam in the mould for having continuous Glass Fiber Mat 5 that tiles, obtain pouring mould Base.
Step 4：After moulded from foam reacts 20 minutes, mould is put into air dry oven under the conditions of 70 DEG C and cures 24h, Foamed material after the demoulding, then, the epidermis of the foamed material is cut off using high-speed cutting machine, obtain LNG ship grad enhancement Heat-insulating material.
Embodiment 6：
From raw material：It is PPG, poly methylene poly phenyl poly isocyanate, tertiary amine catalyst, organotin catalyzed Agent, TDE, antimony oxide, foam stabiliser, HFC-365mfc, continuous Glass Fiber Mat 5.
From the mass ratio of raw material：100：150：0.2：0.9：84：21：1.5：25：40.
Step 1：By PPG, TDE powder, antimony oxide powder and continuous Glass Fiber Mat 5 It is placed in air dry oven under the conditions of 90 DEG C and dries 24h, it is standby is then cooled to room temperature.
Step 2：Standby continuous Glass Fiber Mat 5 is cut into after the shape of suitable mould uniformly after step 1 is handled It is laid in mold bottom.
Step 3：By foam stabiliser, tertiary amine catalyst, organic tin catalyst, TDE, three oxidations two Antimony and HFC-365mfc, which are added in PPG, to be mixed, and is stirred, and it is more to be then rapidly added polymethylene polyphenyl again Isocyanates, 30~50s is stirred, be subsequently poured into moulded from foam in the mould for having continuous Glass Fiber Mat 5 that tiles, obtain pouring mould Base.
Step 4：After moulded from foam reacts 20 minutes, mould is put into air dry oven under the conditions of 70 DEG C and cures 24h, Foamed material after the demoulding, then, the epidermis of the foamed material is cut off using high-speed cutting machine, obtain LNG ship grad enhancement Heat-insulating material.
Preferably to embody the technique effect of the present invention, there is provided comparative example is as follows, and continuous glass is not used in comparative example Glass fibrofelt 5.
Comparative example 1：
From raw material：It is PPG, poly methylene poly phenyl poly isocyanate, tertiary amine catalyst, organotin catalyzed Agent, TDE, antimony oxide, foam stabiliser, HFC-365mfc
From the mass ratio of raw material：100：150：0.2：0.9：84：21：1.5：40.
Preparation process：PPG, TDE powder and antimony oxide powder are put into air dry oven 24h is dried under the conditions of 90 DEG C, it is stand-by to be cooled to room temperature.By HFC-365mfc, tertiary amine catalyst, organotin catalysts, ten bromines Diphenylethane, antimony oxide and foam stabiliser are added in PPG after being weighed according to formula and stirred, then Poly methylene poly phenyl poly isocyanate is rapidly added, moulded from foam in square dies is poured into after stirring 30~50s, is poured Mold base；Mould is put into air dry oven and 24h is cured under the conditions of 70 DEG C by reaction after 20 minutes, and the then demoulding obtains grad enhancement Material.
Comparative example 2：
From raw material：It is PPG, poly methylene poly phenyl poly isocyanate, tertiary amine catalyst, organotin catalyzed Agent, TDE, antimony oxide, foam stabiliser, HFC-365mfc
From the mass ratio of raw material：100：150：0.2：0.9：84：21：1.5：30.
Preparation process：PPG, TDE powder and antimony oxide powder are put into air dry oven 24h is dried under the conditions of 90 DEG C, it is stand-by to be cooled to room temperature.By HFC-365mfc, tertiary amine catalyst, organotin catalysts, ten bromines Diphenylethane, antimony oxide and foam stabiliser are added in PPG after being weighed according to formula and stirred, then Poly methylene poly phenyl poly isocyanate is rapidly added, moulded from foam in square dies is poured into after stirring 30~50s, is poured Mold base；Mould is put into air dry oven and 24h is cured under the conditions of 70 DEG C by reaction after 20 minutes, and the then demoulding obtains grad enhancement Material.
In above example or comparative example, the sample of different continuous glass-fiber felt contents is defined as along LNG ship ladder Spend the sample that the gradient direction of heat-insulating material obtains.The present invention comments method to estimate as follows for grad enhancement material property, and (sample takes From the different parts of gradient heat-insulating material gradient direction)：
Apparent density：By grad enhancement material cut growth 50mm, wide 50mm, high 50mm sample, measure and record it Quality and volume, and tested according to GB/T6343-2009.
Compression performance：Tested according to GB/T 8813-2008, tester is tested for Zwick-Z010 universal materials Machine, German Zwick/Roell companies.Grad enhancement material is cut into 50mm × 50mm × 50mm cube, test compression Speed is 5mm/min, stops test when the thickness for being compressed to sample is changed into the 85% of original depth.Compressive strength is defined as shape Become 10% before maximal compressed stress for value.
Tensile property is tested：Tester is Zwick-Z010 universal testing machines, German Zwick/Roell companies. Regulation of the method for testing according to ASTM D1623-09, the cutting of grad enhancement material is polished into specific dumbbell shaped sample, tested When rate of extension be 1.3mm/min.
Limited oxygen index LOI：Tester is JF-3 type oxygen index instruments, Jiangning, Nanjing Analytical Instrument Co., Ltd.Test Method, need to be by grad enhancement material 130mm × 10mm × 10mm sample according to the regulation requirement in GB/T 2406.2-2009 Bar, it is put into position to be measured.After instrumental correction, its nitrogen, oxygen gas mixture stream proportioning are adjusted, test sample is just tieed up in the gas flow Hold the limited oxygen index of the concentration of oxygen required during burning, as material.
Horizontal firing is tested：Tester is horizontal firing analyzer, Jiangning, Nanjing Analytical Instrument Co., Ltd.Test side Method is determined according to GB/T8332-2008, and grad enhancement material is first made to 150mm × 25mm × 13mm batten, close to point Fire and rule at the 25mm of one end.Batten is lighted according to the regulation of standard, records the burning extent and self-extinguishing time of sample.Each Sample retest 5 times, results averaged.
Heat-insulating property：By grad enhancement material cut growth 300mm, wide 300mm, high 50mm sample, according to ASTM C518 or ISO 8301, its thermal conductivity factor is tested using the hot-fluid conductometer HFM436 of German Nai Chi companies, will test during measurement Temperature is set to 25 DEG C, and the upper and lower plates temperature difference is set to 20 DEG C.
Rate of closed hole：By grad enhancement material cut growth 30mm, wide 30mm, high 60mm sample, measure and record its matter Amount and volume, are tested according to GB/T 10799-2008, and tester is that the full-automatic real densities of ULTRAPYC1200e are opening/closing Porosity analyzer, Kang Ta companies of the U.S..Test pressure is 3Psi, and pattern is set to repeatedly test, single sample retest 6 times, Take the value in error 1%.
Linear expansion coefficient：Grad enhancement material is cut and is polished into a diameter of 5mm with sand paper, length is 25mm circle Cylindrical samples, and according to ASTM E228 or DIN 51045-1, tested, tested using NETZSCH ExpedisSupreme Temperature range is -170~+20 DEG C, test load 10mN.
The content measuring of continuous Glass Fiber Mat 5：Calcination method is employed to determine quantifier elimination glass in grad enhancement material Distribution situation, grad enhancement material is cut into 3 × 3 × 3cm 3 pieces of fritter sample, weighs respectively and records its quality. 3h is calcined 800 DEG C in Muffle furnace, under the conditions of air atmosphere, more bright glass has been calcined in recovery.On assay balance respectively Claim its quality, divided by before calcining sample quality, take 3 result average values, you can obtain the content of glass in sample.
The performance data of heat-insulating material prepared by embodiment and comparative example assesses such as following table：
Performance rating data is shown：
1st, in embodiment 1-3, the sample enhancing effect of the embodiment 3 of glass fiber content 9.7% is optimal.With comparative example 1 is compared, and the compressive strength of thickness direction is lifted to 0.75MPa, lifting 29% from 0.58MPa；The modulus of compressibility of thickness direction From 20.50MPa liftings to 27.27MPa, lifting 33%.The tensile strength of thickness direction is lifted to 1.23MPa from 0.72MPa, Lifting 71%；The tensile strength in vertical thickness direction is lifted to 1.45MPa, lifting 104% from 0.71MPa；The drawing of thickness direction Modulus is stretched from 18MPa liftings to 35MPa, lifting 94%；The stretch modulus in vertical thickness direction is lifted to 52MPa from 16MPa, is carried Rise 225%.This explanation continuous Glass Fiber Mat 5 is more preferable to the enhancing effect in gradient heat-insulating material vertical thickness direction.Implementing In example 4-6, the sample enhancing effect of the embodiment 6 of glass fiber content 9.5% is best.Compared with comparative example 2, thickness direction Compressive strength is lifted to 1.91MPa, lifting 58% from 1.21MPa；The modulus of compressibility of thickness direction from 31.60MPa lifted to 47.12MPa, lifting 49%.The tensile strength of thickness direction is lifted to 2.28MPa, lifting 73% from 1.32MPa；It is vertical thick The tensile strength for spending direction is lifted to 2.82MPa, lifting 117% from 1.30MPa；The stretch modulus of thickness direction carries from 34MPa It is raised to 85MPa, lifting 150%；The stretch modulus in vertical thickness direction is lifted to 126MPa, lifting 294% from 32MPa.Explanation Continuous Glass Fiber Mat 5 is more preferable to the enhancing effect of highdensity gradient heat-insulating material.In addition, mechanical property, is particularly stretched The raising of performance may also suppress material interface and the internal extension that there may be defect.
2nd, because the addition of glass causes PUR linear expansion coefficient to reduce, and PUR plates glass fiber content and the high side of density Linear expansion coefficient is lower, and this is installed facing to secondary screen-wall metallic walls, can make the linear expansion coefficient of foam and metal (with 304 not Steel become rusty exemplified by -50 DEG C, its thermal coefficient of expansion is about 16*10-6mm/mm/ DEG C, and is varied with temperature less) difference subtracted It is small, thus in adiabatic system temperature change, it can avoid the occurrence of because differences in expansion causes heat insulation layer to come off the phenomenon of damage.Can be with See, when density of material is 70kg/m3During left and right, with the increase of the content of continuous Glass Fiber Mat 5, the linear expansion coefficient of material Constantly reduce, the 57.68*10-6mm/mm/ in embodiment 3 has been reduced to from 68.12*10-6mm/mm/ DEG C in comparative example 1 ℃；When density of material is 115kg/m3During left and right, with the increase of the content of continuous Glass Fiber Mat 5, the linear expansion coefficient of material 24.21*10-6mm/mm/ DEG C be reduced to from 40.23*10-6mm/mm/ DEG C in comparative example 2 in embodiment 6.Therefore, glass Fine addition can significantly increase the mechanical property of PUR plates.Because Graded Density and gradient glass fiber content, glass be present in PUR plates Content and the high side mechanical strength of density can be higher.It will be installed at the tank body low temperature facing to -163 DEG C, by glass fiber content Low and low density side is towards at normal temperature, as shown in Figures 2 and 3 so that parts of the PUR at low temperature in shrinkage stress and LNG is rocked to be less susceptible to be destroyed under impact, enhances the stability of adiabatic system.Meanwhile the addition of glass also make it that PUR's is tough Property and mechanical strength increase so that the influence of thermal stress caused by thermograde and differential deformation greatly reduces, extend absolutely The service life of hot systems.
3rd, the addition of glass would generally make PUR thermal conductivity factor increase with glass fiber content and rise, and use grad enhancement Insulation material prepared by method, while can guarantee that mechanics enhancing effect, due to simply in the big position glass of material thermal stress Content is high and relatively low in the small position glass fiber content of thermal stress, and glass dosage is greatly lowered, so that material integral heat insulation Can be added by glass be influenceed to fall below minimum, decreased material and prepared cost.
Preferred embodiment of the invention described in detail above.It should be appreciated that the ordinary skill of this area is without wound The property made work can makes many modifications and variations according to the design of the present invention.Therefore, all technician in the art Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea Scheme, all should be in the protection domain being defined in the patent claims.

Claims (10)

  1. A kind of 1. LNG ship grad enhancement heat-insulating material, it is characterised in that
    Component includes PPG, polyisocyanates, foaming agent, foam stabiliser, catalyst, fire retardant and continuous glass fibers Tie up felt；
    The PPG is 100 with the polyisocyanates mass ratio：140~160；
    The PPG is 100 with the foaming agent mass ratio：25~50；
    The PPG is 100 with the foam stabiliser mass ratio：1.5~2；
    The catalyst includes tertiary amine catalyst and organic tin catalyst, and the PPG is catalyzed with the tertiary amines Agent mass ratio is 100：0.2, the PPG is 100 with the organic tin catalyst quality ratio：0.9~1；
    The fire retardant includes bromide fire retardant and Sb system fire retardant, the PPG and the bromide fire retardant mass ratio For 100：80~85, the PPG is 100 with the Sb system fire retardant mass ratio：20~25；
    The PPG is 100 with the continuous Glass Fiber Mat mass ratio：10~40.
  2. A kind of 2. LNG ship grad enhancement heat-insulating material as claimed in claim 1, it is characterised in that the PPG Using sucrose as initiator, the sucrose hydroxyl value is 480~500mgKOH/g.
  3. A kind of 3. LNG ship grad enhancement heat-insulating material as claimed in claim 1, it is characterised in that the polyisocyanates For poly methylene poly phenyl poly isocyanate, the poly methylene poly phenyl poly isocyanate degree of functionality is 2.6~3.1, NCO matter It is 30.0%~32.0% to measure fraction.
  4. 4. a kind of LNG ship grad enhancement heat-insulating material as claimed in claim 1, it is characterised in that the foaming agent is HFC Class foaming agent.
  5. A kind of 5. LNG ship grad enhancement heat-insulating material as claimed in claim 1, it is characterised in that the foam stabiliser For the silicon class surfactant of the polyether-modified structure containing Si-C.
  6. A kind of 6. LNG ship grad enhancement heat-insulating material as claimed in claim 1, it is characterised in that the bromide fire retardant For environmentally friendly TDE, the Sb system fire retardant is antimony oxide, and average grain diameter is 0.7 μm.
  7. A kind of 7. LNG ship grad enhancement heat-insulating material as claimed in claim 1, it is characterised in that the continuous glass fibers Infiltrated dose of glass fiber bundle surface and silane coupler have carried out surface modification in dimension felt.
  8. 8. a kind of LNG ship grad enhancement heat-insulating material as claimed in claim 1, it is characterised in that the grad enhancement is exhausted Hot material density is 70~130kg/m3, limited oxygen index is more than 30%.
  9. 9. the short process making method of a kind of LNG ship grad enhancement heat-insulating material as described in claim 1~8 is any, it is special Sign is, comprises the following steps：
    Step 1：The PPG, the fire-retardant powder and the continuous Glass Fiber Mat are placed in air dry oven In 24h is dried under the conditions of 90 DEG C, it is standby to be then cooled to room temperature；
    Step 2：The standby continuous Glass Fiber Mat is uniformly put down after being cut into the shape of suitable mould after step 1 is handled It is layered on mold bottom, the fire retardant includes the bromide fire retardant and the Sb system fire retardant, the PPG, described The mass ratio of bromide fire retardant, the Sb system fire retardant and the continuous Glass Fiber Mat is 100：80~85：20~25：10~ 40；
    Step 3：The foam stabiliser, the tertiary amine catalyst, the organic tin catalyst, the bromine system is fire-retardant Agent, the Sb system fire retardant and the foaming agent, which are added in the PPG, to be mixed, and is stirred, is then added institute Polyisocyanates is stated, is stirred, is subsequently poured into the mould and carries out moulded from foam, obtains pouring mold base, the polyethers is more First alcohol, the foam stabiliser, the tertiary amine catalyst, the organic tin catalyst, the bromide fire retardant, the antimony The mass ratio of flame retardant, the foaming agent and the polyisocyanates is 100：1.5~2：0.2：0.9~1：80~85：20 ~25：25~50：140~160；
    Step 4：The mold base that pours is put into air dry oven, cured under 70 DEG C of Conditions Conditions；
    Step 5：After the curing terminates, the mold base that pours is stripped, obtains foamed material, then, using cutting at a high speed Cutting mill cuts off the epidermis of the foamed material, obtains LNG ship grad enhancement heat-insulating material.
  10. 10. a kind of short process making method of LNG ship grad enhancement heat-insulating material as claimed in claim 9, its feature exist In the heat-insulating material of LNG ship grad enhancement described in step 5 density is 70~130kg/m3, limited oxygen index is more than 30%.
CN201710562862.7A 2017-07-11 2017-07-11 A kind of LNG ship grad enhancement heat-insulating material and its short process making method Pending CN107459617A (en)

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CN111574673A (en) * 2020-06-03 2020-08-25 湖南省普瑞达内装材料有限公司 Environment-friendly heat-conducting polyurethane foam, preparation method thereof and adhesive tape
CN112816392A (en) * 2021-03-11 2021-05-18 厦门厦钨新能源材料股份有限公司 Analytical test method for closed-cell porosity of crystalline substance
CN113861661A (en) * 2021-09-28 2021-12-31 浙江联洋新材料股份有限公司 Fiber-reinforced high-molecular rigid foam and production process thereof
CN117261374A (en) * 2023-09-28 2023-12-22 洛阳双瑞橡塑科技有限公司 Composite material type laminated wood for LNG ship and preparation method thereof

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CN101578312A (en) * 2007-01-09 2009-11-11 巴斯夫欧洲公司 Water-blown rigid foams for the insulation of liquefied natural gas tanks
CN104829812A (en) * 2015-05-06 2015-08-12 上海交通大学 Flame-retardant hard polyurethane thermal-insulation foam material and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108264754A (en) * 2017-12-29 2018-07-10 美瑞新材料股份有限公司 A kind of Thermoplastic polyurethane elastomer foam material with density gradient and preparation method thereof
CN111574673A (en) * 2020-06-03 2020-08-25 湖南省普瑞达内装材料有限公司 Environment-friendly heat-conducting polyurethane foam, preparation method thereof and adhesive tape
CN112816392A (en) * 2021-03-11 2021-05-18 厦门厦钨新能源材料股份有限公司 Analytical test method for closed-cell porosity of crystalline substance
CN113861661A (en) * 2021-09-28 2021-12-31 浙江联洋新材料股份有限公司 Fiber-reinforced high-molecular rigid foam and production process thereof
CN117261374A (en) * 2023-09-28 2023-12-22 洛阳双瑞橡塑科技有限公司 Composite material type laminated wood for LNG ship and preparation method thereof

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