CN105237728B

CN105237728B - A kind of material and its rigid foam preparation method for manufacturing rigid foam

Info

Publication number: CN105237728B
Application number: CN201510611901.9A
Authority: CN
Inventors: 陈维敏; 罗金安; 黄杰; 梁倩倩
Original assignee: Sichuan Dongcai Technology Group Co Ltd
Current assignee: Sichuan Dongcai Technology Group Co Ltd
Priority date: 2015-09-23
Filing date: 2015-09-23
Publication date: 2017-12-26
Anticipated expiration: 2035-09-23
Also published as: CN105237728A

Abstract

The invention discloses a kind of material and its rigid foam preparation method for manufacturing rigid foam, it is characterized in that：Take 2.8~3.0, viscosity as 7000~10000 mPaS at 25 DEG C, the mgKOH/g of hydroxyl value 380~450, the PEPA that acid number is 0.1~2 mgKOH/g of high functionality, isocyanates, catalyst 1^#, catalyst 2^#Physical blowing agent, foam stabiliser, and crosslinking agent etc. is raw material, foam stabiliser is used to be compounded for two class organic silicon surfactants, efficient emulsification, two big key technologies of nucleation during rigid foam is processed combine, and prepare compressive strength and bending strength not less than 500KPa, size changing rate（80 DEG C, 48h）Rigid foam not higher than 0.4%.The rigid foam is widely used in the fields such as refrigerating plant and equipment such as building materials, communications and transportation, refrigerator, jelly storehouse.

Description

A kind of material and its rigid foam preparation method for manufacturing rigid foam

Technical field

The invention belongs to the preparation for the material and its foamed plastics for manufacturing rigid foam.It is related to a kind of manufacture hard bubble The material and its rigid foam preparation method of foam plastics, the present invention are prepared high using raw materials such as high-functionality polyester polyols Intensity polyurethane foam plastics, obtained rigid foam are applied to the refrigeration such as building materials, communications and transportation, refrigerator, jelly storehouse The field such as device and equipment.

Background technology

In the prior art, the preparation method of polyurethane rigid foam plastic mainly divides polyester polyols alcohol type and PPG Two kinds of type.Polyester polyol functionality is generally 2.0~2.4 or so.If use polyester polyols alcohol production rigid poly urethanes merely Foamed plastics, because its degree of functionality is relatively low, foam inside crosslinking degree deficiency will be caused and influence the mechanical strength of foamed plastics, And the dimensional stability of foamed plastics is finally influenceed, it serious contraction is easily occurred when applied to building heat preservation field and show As causing foam board easily to be come off from building adhesive surface.Although and the degree of functionality of PPG is higher (generally >=4), (such as the trade mark is 4110 to the simple PPG for use 4 degrees of functionality, and its degree of functionality is 4) to foam, due to PPG Backbone structure be ehter bond, its stronger intramolecular flexibility is sent out by polyethers the mechanical strength of hard polyurethane foam by reducing, and singly It is pure use higher functionality PPG (such as trade mark for N-635,6) its degree of functionality is, on the one hand because its degree of functionality is higher, Foam process is difficult to control, and easily causes foam crosslink density excessive；On the other hand the polyether polyol hydroxyl value of this kind of model compared with High (generally >=450mgKOH/g), compared with the PEPA of equal parts, it will be consumed more using such PPG More isocyanates, not only increase cost, the content of hard section in foam more greatly improved, cause sheet material hair shortcake, embrittlement.For solution Certainly above mentioned problem, the method that existing foaming technique is typically used in mixed way using PPG and PEPA are more to improve The average functionality of first alcohol mixture, and increase using the ester bond inside PEPA the rigidity of material, but the method one Aspect, because the backbone structure of PPG and PEPA is not consistent, the compatibility of the two is poor, in mixed at high speed Often occurs lamination after stirring, this will destroy the regularity of foam structure, and influence the rigidity and its thermal conductivity of foam, another Aspect the method technique is relatively complicated, and cost is higher.

Chinese patent application publication number CN104262596A discloses a kind of high-functionality polyester polyol and its preparation side Method is using high-functionality polyester polyol and carries out foaming by art methods and prepares rigid foam, although institute The mechanical strength of obtained polyurethane rigid foam plastic improves, but also simply reaches building trade standard reluctantly 《JG/T 314—2012》In for hard polyurethane foam composite insulation boards intensity requirement (compressive strength >=150KPa), it is and actual In most industries for the mechanical strength and dimensional stability of foamed plastics have requirements at the higher level (it is general require >= 200KPa), this also causes above-mentioned foamed plastics to have significant limitation in actual applications.Chinese Patent Application No. 200610019610.1 provide it is a kind of prepare high-strength polyurethane foamed plastics with PPG, this method mainly by Increase the mode of inorganic material in formula to improve the intensity of foam, but above-mentioned inorganic material is difficult uniform in mixed process Ground is distributed in PPG system, and the cell density for causing it to be formed in foaming is uneven, easy be open even collapses, Directly influence foam plastic product dimensional stability (foam plastic product prepared by this method, at 20 DEG C, 24 hours conditions Under, dimensional stability ＞ 0.6% (and the foamed plastics prepared according to the inventive method, it is at 80 DEG C, under the conditions of 48 hours, chi Very little stability ＜ 0.5%).Chinese Patent Application No. 200610039944.5 is prepared a kind of biomass-based polynary using rapeseed oil Alcohol, then mixed with other polyethers (or polyester) polyalcohol and prepare hard polyurethane foam to foam, though this method is to reducing cost There is certain effect, but the mechanical strength of the foamed plastics prepared using the method is not high, molded density 37.6kg/m³When compress Intensity also only reaches 203KPa, and which limit the application field of foamed plastics；Secondly, biopolyol is prepared with rapeseed oil, Process is excessively complicated, unstable product quality.

The content of the invention

The purpose of the present invention is intended to overcome above-mentioned deficiency of the prior art, there is provided a kind of material for manufacturing rigid foam Material and its rigid foam preparation method.So as to provide a kind of compressive strength and bending strength not less than 500KPa, size The preparation method of the rigid foam of (80 DEG C, the 48h) polyurethane rigid foam plastics not higher than 0.5% of rate of change.

Present disclosure is：A kind of material for manufacturing rigid foam, it is characterized in that：The material is by component A and B Component forms；

The component A is by the mass parts of high-functionality polyester polyol 80~120, catalyst 1^#0.5~0.7 mass parts, thing Haircut infusion 20~35 mass parts, the mass parts of water 0.3~0.6, the mass parts of foam stabiliser 1~1.5 and the matter of crosslinking agent 4~6 Measure (uniform) the mixing composition of part；

The B component is by the mass parts of isocyanates 84~126, catalyst 2^#0.1~0.3 mass parts (uniform) mixing group Into；

The high-functionality polyester polyol be average functionality be 2.8~3.0, viscosity be 7000 at 25 DEG C~ 10000mPaS, 380~450mgKOH/g of hydroxyl value, the PEPA that acid number is 0.1~2mgKOH/g；

The catalyst 1^#It is (aminated compounds product) PT303, BX405, PT302, triethylene diamine, triethylamine, three Mixture more than one or both of monoethanolamine, diethylenetriamine and N, N- dimethyl cyclohexyl amine；

The physical blowing agent is one or both of pentamethylene, isopentane, HCFC-141b and HFC-245fa； HCFC-141b, HFC-245fa are that the common physical blowing agent product in China Chemical Industry market, production enterprise have：Zhejiang hugeization Limited company, Jiangsu Bluestar Green Technology Co., Ltd., middleization blue sky Honeywell new material Co., Ltd；

The foam stabiliser is one or more and nucleation class in emulsification class organic silicon surfactant One or more mixtures formed in organic silicon surfactant；The emulsification class organic silicon surfactant is B- 84803rd, B-8534, AK8818, AK8811, AK8809, the nucleation class organic silicon surfactant are B-84805, B- 8545、SILBYK-9231、AK8882；Wherein：B-84803, B-8534, B-84805, B-8545 win for Germany creates industrial group Foam stabiliser product, SILBYK-9231 are German Bi Ke chemical companies foam stabiliser product, AK8818, AK8882, AK8811, AK8809 are that the common foam stabiliser product in China Chemical Industry market, production enterprise have：Learn in Mei Si Dehua, Jiangsu Limited company；

The crosslinking agent is one or both of glycerine, pentaerythrite, trimethylolpropane, sorbierite and sucrose Mixture above；

The isocyanates is poly methylene poly phenyl poly isocyanate (abbreviation PAPI), toluene di-isocyanate(TDI) (abbreviation TDI one or two kinds of mixtures)；

The catalyst 2^#It is (organic metal class compound products) MB20, T-120, T-125, stannous octoate and two Mixture more than one or both of dibutyl tin laurate；

Foamed time of the material at 60~90 DEG C is 17~24 seconds, and gel time is 53~62 seconds, does not glue the time For 72~83 seconds；

Using 50 ± 1 ㎏ of apparent density/m of the rigid foam of the material manufacture³When, size changing rate (80 DEG C, It is 48h) 0.3% ± 0.04%, compressive strength and bending strength are not less than 500KPa, and color is white.

In present disclosure：The high-functionality polyester polyol is preferably that the trade mark in China Chemical Industry market is PS- (production enterprise has 4027 PEPA product：Nanjing Nanjing Si Taipan Chemical Co., Ltd.s), it is also possible to using existing There is the homemade PEPA for meeting above-mentioned condition of technology.

In present disclosure：The catalyst 1^#The amine preferably provided for US Air gasification chemical product Co., Ltd Compound products PT303, BX405 and PT302.

In present disclosure：The crosslinking agent is preferably glycerine and the mixture of pentaerythrite.

In present disclosure：The catalyst 2^#Preferably provided for US Air gasification chemical product Co., Ltd organic Metal based compound product MB20, T-120 and T-125.

In present disclosure：Foamed time of the material at 60~90 DEG C is 17~24 seconds, gel time 53 ~62 seconds, the not viscous time was 72~83 seconds.

In present disclosure：Using 50 ± 1 ㎏ of apparent density/m of the rigid foam of the material manufacture³When, (80 DEG C, 48h) of size changing rate is 0.3% ± 0.04%, and compressive strength and bending strength are not less than 500KPa, and color is white Color.

The present invention another content be：A kind of preparation method of rigid foam, it is characterized in that step is：

A, component A is prepared：Take 80~120 mass parts high-functionality polyester polyols, 0.5~0.7 mass parts of catalyst 1^#、 20~35 mass parts physical blowing agents, 0.3~0.6 mass parts water, 1~1.5 mass parts foam stabiliser, the crosslinking of 4~6 mass parts Agent, component A batch can is placed in, high-speed stirred mixes 20~30 minutes, and component A is made, standby；

B, B component is prepared：Take the mass parts of isocyanates 84~126, catalyst 2^#0.1~0.3 mass parts, are placed in B component Batch can, high-speed stirred mix 20~30 minutes, and B component is made, standby；

C, rigid foam is prepared：Component A and B component are injected separately into foaming machine, high-speed stirred 15~40 seconds, controlled Temperature of charge processed is injected into inwall and scribbles releasing agent and be preheating to temperature under conditions of 25~30 DEG C, relative humidity ＜ 70% Spend in the mould for 60~90 DEG C, then the rigid foam of moulding by casting is put into 90~120 DEG C of baking ovens together with mould In, room temperature is cooled to after drying 4~6 hours, opens mould, peels off and takes out white article, is obtained rigid foam.

Foamed time of the material that the component A and the B component are formed at 60~90 DEG C is 17~24 seconds, during gel Between be 53~62 seconds, the not viscous time is 72~83 seconds.

50 ± 1 ㎏ of apparent density/m of the obtained rigid foam³When, size changing rate (80 DEG C, 48h) is 0.3% ± 0.04%, compressive strength and bending strength are not less than 500KPa, and color is white.

In another content of the present invention：High-functionality polyester polyol described in step a is preferably China Chemical Industry market The trade mark be PS-4027 PEPA product (production enterprise has：Nanjing Nanjing Si Taipan Chemical Co., Ltd.s), Can be with using the homemade PEPA for meeting above-mentioned condition of prior art.

In another content of the present invention：Catalyst 1 described in step a^#It is preferably the US Air gasification limited public affairs of chemical product Aminated compounds product PT303, BX405 and the PT302 provided is provided.

In another content of the present invention：Crosslinking agent described in step a is preferably glycerine and the mixture of pentaerythrite.

In another content of the present invention：Catalyst 2 described in step b^#It is preferably the US Air gasification limited public affairs of chemical product Organic metal class compound products MB20, T-120 and the T-125 provided is provided.

Compared with prior art, the present invention has following features and beneficial effect：

(1) present invention is compounded two class organic silicon surfactants by using foam stabiliser, in foam stabilization The main function of a kind of organic silicon surfactant in agent：First, efficiently emulsify, process of such activating agent in high-speed stirred In, component A and B component can not only be made easily to be well mixed, effective affecting acreage increase；Second, in foaming process, A can be made Catalyst 1 in component^#With the catalyst 2 in B component^#It is more evenly distributed in component A and B component compound, to improve catalysis Reaction effect.Improve the effective rate of utilization of catalyst, usage amount is reduced to 0.32%, and general minimum use under prior art Measure and be：PEPA is used to use PPG for 0.52% as 0.33%；Third, inspire the initial stage to be formed in foam During, due to catalyst 1^#With catalyst 2^#Distribution is more uniform, and the foam structure of its foam is more regular, and arrangement is also presented More in order and it is fine and close；

The main function of another kind of organic silicon surfactant in foam stabiliser：First, nucleation, component A and B groups The mixed material divided is in high-speed agitating process, and water takes the lead in and isocyanates carries out foamable reaction and releases CO₂, and then polyalcohol Gel reaction is proceeded by with isocyanates, the heat that at this moment foaming and gel reaction are discharged forces physical blowing agent rapid Gasification, its CO released with foamable reaction₂Numerous small bubbles are collectively forming, these small bubbles are referred to as complex, It is the core that foam structure is formed in foamed material；Second, this kind of organic silicon surfactant can also effectively reduce foamable reaction system The surface tension of system, this makes to be dispersed in physical blowing agent and CO in reaction system₂In whole foaming and gel process It is more likely formed complex；Third, the pressure differential of adjacent bubbles in complex can be reduced, the trend that bubble becomes big is reduced, this makes complex not Be broken into it is long then ultimately form foam structure during, one side complex is not easy brokenly bubble, and on the other hand it can arrange more Add even compact, and ultimately form the symmetrical structure (see Figure of description 1 and 2) of polygon or circle with comparison rule, This structure not only can effectively prevent foamed open cell, collapse, and more because it is relatively perfect geometrically symmetric, can be carried when being pressurized larger The destructive power of amplitude, therefore the mechanical property of foam can be greatly improved；

(2) present invention passes through amines catalyst (catalyst 1 in foaming system^#) and organometallic catalysts (catalysis Agent 2^#) compounding, not only effectively improve catalyst activity, shorten the time of foaming and gel, and be significantly increased The crosslink density of molecular network structure during foam post curing, finally realizes the skill for greatly promoting foamed plastics rigid nature Art target；Its result see the table below 1,2：

Table 1：The material of the present invention and catalyst amount, the foaming system Contrast on effect table of existing product

Table 2：The foam performance contrast table that the present invention is prepared with prior art

(3) present invention compounds other polyalcohols as crosslinking agent in foaming system using glycerine, by with isocyanates Reaction, it can be by the carbamate segment formed in foaming process, urea groups segment, allophanate segment and biuret chain The groups such as section are crosslinked together, form finer and close T-shaped network structure, and the Mechanics of Machinery that this can dramatically increase foamed plastics is strong Degree；

(4) present invention is only using PEPA as major ingredient, and the foam sent is with regard to that can meet or exceed with polyether polyols Alcohol is the mechanical performance for the foamed plastics that major ingredient is sent, while also obtain good dimensional stability, greatly reduces foam Plastics cost, it is fully able to the application for substituting PPG in some fields；

(5) present invention process is simple, is easy to industrialized production, and whole process three wastes produce, and meet environmental requirement, practical Property is strong.

Brief description of the drawings

Fig. 1 be use polyurethane rigid foam plastic foam structure figure produced by the present invention, foam density be 49.51 ㎏/ m³, shot in March, 2015 with SEM, model JSM 9600, Jeol Ltd.'s production；

Fig. 2 be use polyurethane rigid foam plastic foam structure figure produced by the present invention, foam density be 102.47 ㎏/ m³, shot in November, 2014 with SEM, model JSM 9600, Jeol Ltd.'s production；

Fig. 3 is as the polyurethane rigid foam plastic obtained by foam stabiliser using single organic silicon surfactant Foam structure figure, foam density are 51.38 ㎏/m³, shot in April, 2015 with SEM, model JSM9600, Jeol Ltd. produces；

Foam involved by attached Fig. 1 and 2 is steady as its foam using two or more organic silicon surfactants compounding Determine agent, not only A, B component and catalyst 1^#With catalyst 2^#, foaming agent mix more fully, uniformly, while foam into Nuclearity is also more good, and therefore, foam structure described in attached Fig. 1 and 2 is not only fine and close, and more regular hexagon is presented respectively And ellipse；And the foam involved by accompanying drawing 3 be using single organic silicon surfactant as its foam stabiliser, its Raw material mixing uniformity and foam into poor in terms of nuclearity, therefore, foam structure described in Figure of description 3 is simultaneously irregular, Abscess arrangement is also more loose.

Embodiment

The invention will be further described for example given below plan, but is not to be construed as to the scope of the present invention Limitation, some nonessential improvement and tune that person skilled in art makes according to the content of the invention described above to the present invention It is whole, still fall within protection scope of the present invention.

Part I embodiments of the invention 1~10

Embodiment 1：

(1) prepared by component A：Take the 80 ㎏ high-functionality polyester polyol (trades mark：PS-4027), 0.5 ㎏ catalyst 1^#(matter It is PT303 to measure ratio：BX405=2：3), 20 ㎏ HCFC-141b, 0.3 ㎏ water, 1 ㎏ foam stabilisers (mass ratio B84803： AK8818：SILBYK-9231=3：3：4), (mass ratio is glycerine to 4 ㎏ crosslinking agents：Pentaerythrite=1：1), it is placed in component A material Tank, high-speed stirred 20 minutes are standby.

(2) prepared by B component：Take 84 ㎏ isocyanates TDI, 0.1 ㎏ catalyst 2^#(mass ratio MB20：T-120=1： 1) B component batch can, is placed in, high-speed stirred 20 minutes is standby.

(3) it is prepared by rigid foam shaping：Component A and B component are injected separately into foaming machine, high-speed stirred 15 seconds, Material temperature is controlled under conditions of 25 DEG C or so, relative humidity ＜ 70%, inwall is injected into and coats releasing agent and be preheating to 60 DEG C Mould in.The foamed plastics of moulding by casting is put into 90 DEG C of baking ovens together with mould again, room temperature is cooled to after 4 hours, Mould is opened, peels off and takes out white article.When the Rigid foam compositions foamed time of component A and B component composition, gel Between, the not viscous time see below table 3.Compressive strength, bending strength and size changing rate in its quality of item performance data see below table 4。

Embodiment 2：

(1) prepared by component A：Take the 85 ㎏ high-functionality polyester polyol (trades mark：PS-4027), 0.55 ㎏ catalyst 1^#(matter It is PT 303 to measure ratio：PT 302=2：3), 23 ㎏ isopentane, 0.35 ㎏ water, 1 ㎏ foam stabilisers (mass ratio B-84803： AK8882：SILBYK-9231=3：3：4), (mass ratio is glycerine to 4 ㎏ crosslinking agents：Trimethylolpropane=1：1) A groups, are placed in Sub-material tank, high-speed stirred 20 minutes are standby.

(2) prepared by B component：Take 89 ㎏ isocyanates PAPI, 0.1 ㎏ catalyst 2^#(mass ratio MB20：T-125=1： 1) B component batch can, is placed in, high-speed stirred 20 minutes is standby.

(3) it is prepared by rigid foam shaping：Component A and B component are injected separately into foaming machine, high-speed stirred 15 seconds, Material temperature is controlled under conditions of 25 DEG C or so, relative humidity ＜ 70%, inwall is injected into and coats releasing agent and be preheating to 65 DEG C Mould in.The foamed plastics of moulding by casting is put into 90 DEG C of baking ovens together with mould again, room is cooled to after 4.5 hours Temperature, mould is opened, peel off and take out white article.The Rigid foam compositions foamed time of component A and B component composition, coagulate Glue time, not viscous time see below table 3.Compressive strength, bending strength and size changing rate in its quality of item performance data are shown in Table 4 afterwards.

Embodiment 3：

(1) prepared by component A：Take the 90 ㎏ high-functionality polyester polyol (trades mark：PS-4027), 0.6 ㎏ catalyst 1^#(matter It is PT 303 to measure ratio：PT 302=1：1), 25 ㎏ pentamethylene, 0.35 ㎏ water, 1 ㎏ foam stabilisers (mass ratio B-8534： AK8882：B-84805=3：4：3), (mass ratio is glycerine to 4 ㎏ crosslinking agents：Sorbierite=1：1) component A batch can, is placed in, at a high speed Stirring 20 minutes, it is standby.

(2) prepared by B component：Take 94 ㎏ isocyanates PAPI, 0.12 ㎏ catalyst 2^#(mass ratio T-120：T-125= 5：7) B component batch can, is placed in, high-speed stirred 20 minutes is standby.

(3) it is prepared by rigid foam shaping：Component A and B component are injected separately into foaming machine, high-speed stirred 25 seconds, Material temperature is controlled under conditions of 26 DEG C or so, relative humidity ＜ 70%, inwall is injected into and coats releasing agent and be preheating to 70 DEG C Mould in.The foamed plastics of moulding by casting is put into 100 DEG C of baking ovens together with mould again, room temperature is cooled to after 5 hours, Mould is opened, peels off and takes out white article.When the Rigid foam compositions foamed time of component A and B component composition, gel Between, the not viscous time see below table 3.Compressive strength, bending strength and size changing rate in its quality of item performance data see below table 4。

Embodiment 4：

(1) prepared by component A：Take the 95 ㎏ high-functionality polyester polyol (trades mark：PS-4027), 0.6 ㎏ catalyst 1^#(matter It is PT 303 to measure ratio：Triethylene diamine=1：2), 27 ㎏ HCFC-141b, 0.4 ㎏ water, 1 ㎏ foam stabilisers (mass ratio B- 8534：AK8811：B-8545=3：4：3), (mass ratio is glycerine to 4.5 ㎏ crosslinking agents：Sucrose=5：4) component A batch can, is placed in, High-speed stirred 20 minutes, it is standby.

(2) prepared by B component：Take 99.5 ㎏ isocyanates (mass ratio PAPI：TDI=5：1), 0.13 ㎏ catalyst 2^# (mass ratio MB20：Dibutyl tin laurate=6：7) B component batch can, is placed in, high-speed stirred 20 minutes is standby.

(3) it is prepared by rigid foam shaping：Component A and B component are injected separately into foaming machine, high-speed stirred 25 seconds, Material temperature is controlled under conditions of 26 DEG C or so, relative humidity ＜ 70%, inwall is injected into and coats releasing agent and be preheating to 80 DEG C Mould in.The foamed plastics of moulding by casting is put into 100 DEG C of baking ovens together with mould again, room temperature is cooled to after 5 hours, Mould is opened, peels off and takes out white article.When the Rigid foam compositions foamed time of component A and B component composition, gel Between, the not viscous time see below table 3.Compressive strength, bending strength and size changing rate in its quality of item performance data see below table 4。

Embodiment 5：

(1) prepared by component A：Take the 100 ㎏ high-functionality polyester polyol (trades mark：PS-4027), 0.6 ㎏ catalyst 1^#(matter It is BX405 to measure ratio：Triethylene diamine=1：2), 27 ㎏ HCFC-141b, 0.45 ㎏ water, 1.15 ㎏ foam stabiliser (mass ratioes For AK 8811：B-8545：SILBYK-9231=8：8：7), (mass ratio is pentaerythrite to 4.5 ㎏ crosslinking agents：Sucrose=4：5), Component A batch can is placed in, high-speed stirred 25 minutes is standby.

(2) prepared by B component：Take 104.5 ㎏ isocyanates (mass ratio PAPI：TDI=1：3), 0.17 ㎏ catalyst 2^# (mass ratio T-120：Dibutyl tin laurate=3：4) B component batch can, is placed in, high-speed stirred 25 minutes is standby.

(3) it is prepared by rigid foam shaping：Component A and B component are injected separately into foaming machine, high-speed stirred 30 seconds, Material temperature is controlled under conditions of 27 DEG C or so, relative humidity ＜ 70%, inwall is injected into and coats releasing agent and be preheating to 80 DEG C Mould in.The foamed plastics of moulding by casting is put into 105 DEG C of baking ovens together with mould again, room temperature is cooled to after 5 hours, Mould is opened, peels off and takes out white article.When the Rigid foam compositions foamed time of component A and B component composition, gel Between, the not viscous time see below table 3.Compressive strength, bending strength and size changing rate in its quality of item performance data see below table 4。

Embodiment 6：

(1) prepared by component A：100 ㎏ are taken to make high-functionality polyester polyol, 0.6 ㎏ 1 by oneself^#Catalyst (mass ratio PT 302：N, N- dimethyl cyclohexyl amine=2：1), 27 ㎏ HFC-245fa, 0.45 ㎏ water, 1.15 ㎏ foam stabilisers (mass ratio B- 84803：AK8809：SILBYK-9231=8：8：7), (mass ratio is trimethylolpropane to 4.5 ㎏ crosslinking agents：Sucrose=4：5), Component A batch can is placed in, high-speed stirred 25 minutes is standby.

(2) prepared by B component：Take 104.5 ㎏ isocyanates (mass ratio PAPI：TDI=3：5), 0.17 ㎏ catalyst 2^# (mass ratio T-120：Dibutyl tin laurate=1：1) B component batch can, is placed in, high-speed stirred 25 minutes is standby.

Embodiment 7：

(1) prepared by component A：105 ㎏ are taken to make high-functionality polyester polyol, 0.6 ㎏ catalyst 1 by oneself^#(mass ratio PT 303：BX 405：N, N- dimethyl cyclohexyl amine=1：1：1), (mass ratio is pentamethylene to 27 ㎏ physical blowing agents：HCFC-141b= 5：4), 0.5 ㎏ water, 1.2 ㎏ foam stabilisers (mass ratio B-8534：AK8811：AK8882：SILBYK-9231=4：6：7： 7), (mass ratio is sorbierite to 5 ㎏ crosslinking agents：Sucrose=1：1) component A batch can, is placed in, high-speed stirred 25 minutes is standby.

(2) prepared by B component：Take 110 ㎏ isocyanates (mass ratio PAPI：TDI=5：1), 0.20 ㎏ catalyst 2^#(matter It is MB20 to measure ratio：T-120：Dibutyl tin laurate=4：4：7) B component batch can, is placed in, high-speed stirred 25 minutes is standby.

(3) it is prepared by rigid foam shaping：Component A and B component are injected separately into foaming machine, high-speed stirred 30 seconds, Material temperature is controlled under conditions of 27 DEG C or so, relative humidity ＜ 70%, inwall is injected into and coats releasing agent and be preheating to 85 DEG C Mould in.The foamed plastics of moulding by casting is put into 110 DEG C of baking ovens together with mould again, room temperature is cooled to after 5 hours, Mould is opened, peels off and takes out white article.When the Rigid foam compositions foamed time of component A and B component composition, gel Between, the not viscous time see below table 3.Compressive strength, bending strength and size changing rate in its quality of item performance data see below table 4。

Embodiment 8：

(1) prepared by component A：110 ㎏ are taken to make high-functionality polyester polyol, 0.65 ㎏ catalyst 1 by oneself^#(mass ratio is BX405：PT302：Triethylamine=1：1：1), (mass ratio is isopentane to 30 ㎏ physical blowing agents：HCFC-141b=1：1), 0.55 ㎏ water, 1.25 ㎏ foam stabilisers (mass ratio B-84803：AK8811：AK8882：B-8545=4：6：8：7), 5.5 ㎏ are handed over Joining agent, (mass ratio is glycerine：Pentaerythrite：Trimethylolpropane=5：3：3), it is placed in component A batch can, high-speed stirred 25 minutes, It is standby.

(2) prepared by B component：Take 115.5 ㎏ isocyanates (mass ratio PAPI：TDI=7：2), 0.23 ㎏ catalyst 2^# (mass ratio MB20：T-120：Dibutyl tin laurate=1：1：2) B component batch can, is placed in, high-speed stirred 25 minutes is standby With.

(3) it is prepared by rigid foam shaping：Component A and B component are injected separately into foaming machine, high-speed stirred 35 seconds, Material temperature is controlled under conditions of 28 DEG C or so, relative humidity ＜ 70%, inwall is injected into and coats releasing agent and be preheating to 85 DEG C Mould in.The foamed plastics of moulding by casting is put into 115 DEG C of baking ovens together with mould again, room is cooled to after 5.5 hours Temperature, mould is opened, peel off and take out white article.The Rigid foam compositions foamed time of component A and B component composition, coagulate Glue time, not viscous time see below table 3.Compressive strength, bending strength and size changing rate in its quality of item performance data are shown in Table 4 afterwards.

Embodiment 9：

(1) prepared by component A：115 ㎏ are taken to make high-functionality polyester polyol, 0.67 ㎏ catalyst 1 by oneself^#(mass ratio PT 303：PT 302：Triethylene diamine：N, N- dimethyl cyclohexyl amine=3：3：3：4), (mass ratio is ring penta to 32 ㎏ physical blowing agents Alkane：HFC-245fa=17：15), 0.55 ㎏ water, 1.3 ㎏ foam stabilisers (mass ratio B-8534：AK 8809：AK 8882： SILBYK-9231=5：6：8：7), (mass ratio is glycerine to 6 ㎏ crosslinking agents：Pentaerythrite：Pears alcohol=5：3：4), it is placed in component A Batch can, high-speed stirred 25 minutes are standby.

(2) prepared by B component：Take 121 ㎏ isocyanates (mass ratio PAPI：TDI=3：1), 0.26 ㎏ catalyst 2^#(matter It is MB20 to measure ratio：T-125：Stannous octoate=1：1：2) B component batch can, is placed in, high-speed stirred 25 minutes is standby.

Embodiment 10：

(1) prepared by component A：120 ㎏ are taken to make high-functionality polyester polyol, 0.7 ㎏ catalyst 1 by oneself^#(mass ratio is BX405：PT302：Triethanolamine：Diethylenetriamine=3：3：4：4), (mass ratio is pentamethylene to 35 ㎏ physical blowing agents：Isoamyl Alkane=18：17), 0.6 ㎏ water, 1.5 ㎏ foam stabilisers (mass ratio B-8534：B-84803：AK 8818：AK8882： SILBYK-9231=5：6：7：7：5), (mass ratio is glycerine to 6 ㎏ crosslinking agents：Pentaerythrite：Sorbierite：Sucrose=4：3：2： 3) component A batch can, is placed in, high-speed stirred 30 minutes is standby.

(2) prepared by B component：Take 126 ㎏ isocyanates (mass ratio PAPI：TDI=5：3), 0.3 ㎏ catalyst 2^#(matter It is MB20 to measure ratio：Dibutyl tin laurate：Stannous octoate=8：11：11), it is placed in B component batch can, high-speed stirred 30 minutes, It is standby.

(3) it is prepared by rigid foam shaping：Component A and B component are injected separately into foaming machine, high-speed stirred 40 seconds, Material temperature is controlled under conditions of 30 DEG C or so, relative humidity ＜ 70%, inwall is injected into and coats releasing agent and be preheating to 90 DEG C Mould in.The foamed plastics of moulding by casting is put into 120 DEG C of baking ovens together with mould again, room temperature is cooled to after 6 hours, Mould is opened, peels off and takes out white article.When the Rigid foam compositions foamed time of component A and B component composition, gel Between, the not viscous time see below table 3.Compressive strength, bending strength and size changing rate in its quality of item performance data see below table 4。

Part II comparative example 1~9

Comparative example 1：

It is prepared by (1) first component：Take 100 ㎏ PEPAs (Nanjing Nanjing Si Taipan Chemical Co., Ltd.s trade mark：PS- 2412), 0.9 ㎏ triethylene diamines, 30 ㎏ HCFC-141b, 0.5 ㎏ water, 1.5 ㎏ B-84803, are placed in component A batch can, at a high speed Stirring 25 minutes, it is standby.

It is prepared by (2) second components：100 ㎏ isocyanates PAPI are taken, 0.3 ㎏ stannous octoates, are placed in B component batch can, at a high speed Stirring 25 minutes, it is standby.

(3) prepared by foam molding：First component and the second component are injected separately into foaming machine, high-speed stirred 30 Second, control material temperature is injected into inwall and coats releasing agent and be preheating to 80 under conditions of 25 DEG C or so, relative humidity ＜ 70% DEG C mould in.The foamed plastics of moulding by casting is put into 110 DEG C of baking ovens together with mould again, room is cooled to after 5 hours Temperature, mould is opened, peel off and take out white article.During the common foams composition foaming of the first component and the second component composition Between, gel time, not viscous time see below table 3.Compressive strength, bending strength and change in size in its quality of item performance data Rate sees below table 4.

Comparative example 2：

It is prepared by (1) first component：Take 100 ㎏ PEPAs (Nanjing Nanjing Si Taipan Chemical Co., Ltd.s trade mark：PS- 3152), 0.85 ㎏ N, N- dimethyl cyclohexyl amines, 30 ㎏ HCFC-141b, 0.5 ㎏ water, 1.5 ㎏ AK8811, are placed in component A material Tank, high-speed stirred 25 minutes are standby.

It is prepared by (2) second components：100 ㎏ isocyanates TDI are taken, 0.45 ㎏ stannous octoates, are placed in B component batch can, at a high speed Stirring 25 minutes, it is standby.

(3) foam molding preparation process is identical with comparative example 1.The regular-type foam of first component and the second component composition Plastics composite foamed time, gel time, not viscous time see below table 3.It is compressive strength in its quality of item performance data, curved Qu Qiangdu and size changing rate see below table 4.

Comparative example 3：

It is prepared by (1) first component：Take 100 ㎏ PEPAs (Nanjing Nanjing Si Taipan Chemical Co., Ltd.s trade mark：PS- 2352), 0.95 ㎏ triethanolamines, 30 ㎏ pentamethylene, 0.5 ㎏ water, 1.5 ㎏ AK8882, component A batch can, high-speed stirred 25 are placed in Minute, it is standby.

It is prepared by (2) second components：100 ㎏ isocyanates PAPI are taken, 0.4 ㎏ stannous octoates, are placed in B component batch can, at a high speed Stirring 25 minutes, it is standby.

Comparative example 4：

It is prepared by (1) first component：Take 100 ㎏ PEPAs (the Shandong China really high-tech adhesive Co., Ltd trade mark： 3150-6), 1.15 ㎏ triethylamines, 30 ㎏ isopentane, 0.5 ㎏ water, 1.5 ㎏ B-8534, component A batch can, high-speed stirred 25 are placed in Minute, it is standby.

It is prepared by (2) second components：Take 100 ㎏ isocyanates (mass ratio PAPI：TDI=1：2), 0.35 ㎏ tin dilaurates Dibutyl tin, is placed in B component batch can, and high-speed stirred 25 minutes is standby.

Comparative example 5：

It is prepared by (1) first component：Take 100 ㎏ PEPAs (the Si Kerui polyurethane Co., Ltd trade mark：SKR-400C), 1.5 ㎏ diethylenetriamines, 30 ㎏ HFC-245fa, 0.5 ㎏ water, 1.5 ㎏ AK8809, are placed in component A batch can, high-speed stirred 30 Minute, it is standby.

It is prepared by (2) second components：Take 100 ㎏ isocyanates (mass ratio PAPI：TDI=3：1), 0.3 ㎏ tin dilaurates Dibutyl tin, is placed in B component batch can, and high-speed stirred 30 minutes is standby.

Comparative example 6：

It is prepared by (1) first component：Take 100 ㎏ PPGs (the general trade mark of chemical industry：4110), 0.80 ㎏ triethylenes two Amine, 30 ㎏ HCFC-141b, 0.5 ㎏ water, 1.5 ㎏ B-84803,5 ㎏ glycerine are placed in component A batch can, high-speed stirred 25 minutes, It is standby.

It is prepared by (2) second components：Take 105 ㎏ isocyanates (mass ratio TDI：PAPI=2：3) B component batch can, is placed in, High-speed stirred 25 minutes, it is standby.

Comparative example 7：

It is prepared by (1) first component：Take 100 ㎏ PPGs (the general trade mark of chemical industry：4114), 0.9 ㎏ triethanolamines, 30 ㎏ HCFC-141b, 0.5 ㎏ water, 1.5 ㎏ AK8811,5 ㎏ glycerine are placed in component A batch can, and high-speed stirred 25 minutes is standby.

It is prepared by (2) second components：Take 105 ㎏ isocyanates (mass ratio PAPI：TDI=1：2) B component batch can, is placed in, High-speed stirred 25 minutes, it is standby.

Comparative example 8：

(1) first component：Take 100 ㎏ PPGs (the general trade mark of chemical industry：MN-450), 0.85 ㎏ triethylamines, 30 ㎏ Pentamethylene, 0.5 ㎏ water, 1.5 ㎏ AK8882,5 ㎏ glycerine are placed in component A batch can, and high-speed stirred 25 minutes is standby.

(2) second components：Take 105 ㎏ isocyanates (mass ratio PAPI：TDI=2：3) B component batch can, is placed in, at a high speed Stirring 25, it is standby.

Comparative example 9：

It is prepared by (1) first component：Take 100 ㎏ PPGs (the general trade mark of chemical industry：N-635), 1.0 ㎏ divinyls three Amine, 25 ㎏ HFC-245fa, 0.5 ㎏ water, 1.5 ㎏ B-8534,5 ㎏ glycerine are placed in component A batch can, high-speed stirred 25 minutes, It is standby.

It is prepared by (2) second components：Take 105 ㎏ isocyanates (mass ratio PAPI：TDI=5：2) B component batch can, is placed in, High-speed stirred 25 minutes, it is standby.

The Application Example of technical solution of the present invention is surveyed with the foaming system processing range of comparative example foam plastics composite Examination value such as table 3 below：

Table 3：Embodiment and the foaming system processing range contrast table of comparative example foam plastics composite

Polyurethane foam obtained by rigid foam and comparative example prepared by the Application Example of technical solution of the present invention The performance test value such as table 4 below of foam material：

Table 4：Rigid foam prepared by embodiment and the made polyurethane foam machine tool performance comparison table of comparative example

Note：The PEPA that comparative example 1~5 is taken is market usual products, and its average functionality is 2~2.4, What comparative example 6~9 was taken be in current hard polyurethane foam commonly use PPG model, its average functionality >=4.0.

As can be seen from the above table：Using of the present invention using PEPA as the polyurethane foam plastics prepared by major ingredient In terms of three size changing rate, bending strength and compressive strength mechanical mechanics property tests, its every mechanical property is notable Higher than the test data using the foamed plastics obtained by existing foaming technique.

Embodiment 11：

A kind of material for manufacturing rigid foam, the material are made up of component A and B component；

The component A is by the mass parts of high-functionality polyester polyol 80, catalyst 1^#0.5 mass parts, physical blowing agent 20 Mass parts, the mass parts of water 0.3, the mass parts of foam stabiliser 1 and (uniform) the mixing composition of the mass parts of crosslinking agent 4；

The B component is by the mass parts of isocyanates 84, catalyst 2^#(uniform) the mixing composition of 0.1 mass parts.

Embodiment 12：

The component A is by the mass parts of high-functionality polyester polyol 120, catalyst 1^#0.7 mass parts, physical blowing agent 35 Mass parts, the mass parts of water 0.6, the mass parts of foam stabiliser 1.5 and the mass parts of crosslinking agent 6 (uniform)

Mixing composition；

The B component is by the mass parts of isocyanates 126, catalyst 2^#(uniform) the mixing composition of 0.3 mass parts.

Embodiment 13：

The component A is by the mass parts of high-functionality polyester polyol 100, catalyst 1^#0.6 mass parts, physical blowing agent 28 Mass parts, the mass parts of water 0.5, the mass parts of foam stabiliser 1.2 and the mass parts of crosslinking agent 5 (uniform)

Mixing composition；

The B component is by the mass parts of isocyanates 105, catalyst 2^#(uniform) the mixing composition of 0.2 mass parts.

Embodiment 14~20：

The specific mass parts dosage of each composition in the component A of embodiment 14~20 see the table below：

The specific mass parts dosage of each composition in the B component of embodiment 14~20 see the table below：

Embodiment 21：

A kind of preparation method of rigid foam, step are：

A, component A is prepared：Take 80 mass parts high-functionality polyester polyols, 0.5 mass parts of catalyst 1^#, 20 mass parts things Haircut infusion, 0.3 mass parts water, 1 mass parts foam stabiliser, 4 mass parts crosslinking agents, are placed in component A batch can, high-speed stirred is mixed Close 20 minutes, component A is made, it is standby；

B, B component is prepared：Take the mass parts of isocyanates 84, catalyst 2^#0.1 mass parts, it is placed in B component batch can, high-speed stirring Mixing 20 minutes is mixed, B component is made, it is standby；

C, rigid foam is prepared：Component A and B component are injected separately into foaming machine, high-speed stirred 15 seconds, control thing Material temperature degree is injected into inwall and scribbles releasing agent and be preheating to temperature as 60 DEG C under conditions of 25 DEG C, relative humidity ＜ 70% Mould in, then the rigid foam of moulding by casting is put into 90 DEG C of baking ovens together with mould, is cooled to after drying 6 hours Room temperature, mould is opened, peel off and take out white article, be obtained rigid foam.

Embodiment 22：

A kind of preparation method of rigid foam, step are：

A, component A is prepared：Take 120 mass parts high-functionality polyester polyols, 0.7 mass parts of catalyst 1^#, 35 mass parts Physical blowing agent, 0.6 mass parts water, 1.5 mass parts foam stabilisers, 6 mass parts crosslinking agents, are placed in component A batch can, high-speed stirring Mixing 30 minutes is mixed, component A is made, it is standby；

B, B component is prepared：Take the mass parts of isocyanates 126, catalyst 2^#0.3 mass parts, B component batch can is placed in, at a high speed It is stirred 30 minutes, B component is made, it is standby；

C, rigid foam is prepared：Component A and B component are injected separately into foaming machine, high-speed stirred 40 seconds, control thing Material temperature degree is injected into inwall and scribbles releasing agent and be preheating to temperature as 90 DEG C under conditions of 30 DEG C, relative humidity ＜ 70% Mould in, then the rigid foam of moulding by casting is put into 120 DEG C of baking ovens together with mould, cooled after drying 4 hours To room temperature, mould is opened, peels off and takes out white article, is obtained rigid foam.

Embodiment 23：

A kind of preparation method of rigid foam, step are：

A, component A is prepared：Take 100 mass parts high-functionality polyester polyols, 0.6 mass parts of catalyst 1^#, 27 mass parts Physical blowing agent, 0.4 mass parts water, 1.2 mass parts foam stabilisers, 5 mass parts crosslinking agents, are placed in component A batch can, high-speed stirring Mixing 25 minutes is mixed, component A is made, it is standby；

B, B component is prepared：Take the mass parts of isocyanates 105, catalyst 2^#0.2 mass parts, B component batch can is placed in, at a high speed It is stirred 25 minutes, B component is made, it is standby；

C, rigid foam is prepared：Component A and B component are injected separately into foaming machine, high-speed stirred 15~40 seconds, controlled Temperature of charge processed is injected into inwall and scribbles releasing agent and be preheating to temperature and be under conditions of 28 DEG C, relative humidity ＜ 70% In 75 DEG C of mould, then the rigid foam of moulding by casting is put into 105 DEG C of baking ovens together with mould, after drying 5 hours Room temperature is cooled to, opens mould, peels off and takes out white article, is obtained rigid foam.

Embodiment 24：

A kind of preparation method of rigid foam, step are：

A, component A is prepared：Take 90 mass parts high-functionality polyester polyols, 0.5 mass parts of catalyst 1^#, 26 mass parts things Haircut infusion, 0.4 mass parts water, 1.2 mass parts foam stabilisers, 5 mass parts crosslinking agents, are placed in component A batch can, high-speed stirred Mixing 26 minutes, component A is made, it is standby；

B, B component is prepared：Take the mass parts of isocyanates 96, catalyst 2^#0.2 mass parts, it is placed in B component batch can, high-speed stirring Mixing 26 minutes is mixed, B component is made, it is standby；

C, rigid foam is prepared：Component A and B component are injected separately into foaming machine, high-speed stirred 21 seconds, control thing Material temperature degree is injected into inwall and scribbles releasing agent and be preheating to temperature as 70 DEG C under conditions of 28 DEG C, relative humidity ＜ 70% Mould in, then the rigid foam of moulding by casting is put into 100 DEG C of baking ovens together with mould, cooled after drying 5 hours To room temperature, mould is opened, peels off and takes out white article, is obtained rigid foam.

Embodiment 25：

A kind of preparation method of rigid foam, step are：

A, component A is prepared：Take 80~120 mass parts high-functionality polyester polyols, 0.5~0.7 mass parts of catalyst 1^#、 20~35 mass parts physical blowing agents, 0.3~0.6 mass parts water, 1~1.5 mass parts foam stabiliser, the crosslinking of 4~6 mass parts Agent, component A batch can is placed in, high-speed stirred mixes 20~30 minutes, and component A is made, standby；The specific mass parts dosage of each component With any in embodiment 14~20, omission；

B, B component is prepared：Take the mass parts of isocyanates 84~126, catalyst 2^#0.1~0.3 mass parts, are placed in B component Batch can, high-speed stirred mix 20~30 minutes, and B component is made, standby；The specific mass parts dosage of each component with embodiment 14~ It is any in 20, omit；

In above-described embodiment 11~25：The high-functionality polyester polyol can be average functionality be 2.8~3.0, The polyester that viscosity is 7000~10000mPaS at 25 DEG C, 380~450mgKOH/g of hydroxyl value, acid number are 0.1~2mgKOH/g is more First alcohol；

In above-described embodiment 11~25：The catalyst 1^#Can be (aminated compounds product) PT303, BX405, PT302, triethylene diamine, triethylamine, triethanolamine, diethylenetriamine and one kind in N, N- dimethyl cyclohexyl amine or two The mixture of the kind above；

In above-described embodiment 11~25：The physical blowing agent can be pentamethylene, isopentane, HCFC-141b and One or both of HFC-245fa；HCFC-141b, HFC-245fa are that the common physical blowing agent in China Chemical Industry market produces Product, production enterprise have：Zhejiang Juhua Co., Ltd., Jiangsu Bluestar Green Technology Co., Ltd., middleization Blue sky Honeywell new material Co., Ltd；

In above-described embodiment 11~25：The foam stabiliser can be in emulsification class organic silicon surfactant One or more mixtures formed in one or more and nucleation class organic silicon surfactant；The emulsification Class organic silicon surfactant is B-84803, B-8534, AK8818, AK8811, AK8809, the nucleation class organosilicon Surfactant is B-84805, B-8545, SILBYK-9231, AK8882；Wherein：B-84803、B-8534、B-84805、B- 8545 win wound industrial group foam stabiliser product for Germany, and SILBYK-9231 is German Bi Ke chemical companies foam stabiliser Product, AK8818, AK8882, AK8811, AK8809 are the common foam stabiliser product in China Chemical Industry market, production enterprise Industry has：Jiangsu Maysta Chemical Co., Ltd.；

In above-described embodiment 11~25：The crosslinking agent can be glycerine, pentaerythrite, trimethylolpropane, sorbierite, And mixture more than one or both of sucrose；

In above-described embodiment 11~25：The isocyanates can be poly methylene poly phenyl poly isocyanate (abbreviation PAPI), one or two kinds of mixtures of toluene di-isocyanate(TDI) (abbreviation TDI)；

In above-described embodiment 11~25：The catalyst 2^#Can be (organic metal class compound products) MB20, T- 120th, mixture more than one or both of T-125, stannous octoate and dibutyl tin laurate；

In above-described embodiment 11~25：The high-functionality polyester polyol is preferably that the trade mark in China Chemical Industry market is (production enterprise has PS-4027 PEPA product：Nanjing Nanjing Si Taipan Chemical Co., Ltd.s), it is also possible to use The homemade PEPA for meeting above-mentioned condition of prior art.

In above-described embodiment 11~25：The catalyst 1^#Preferably gasify what chemical product Co., Ltd provided for US Air Aminated compounds product PT303, BX405 and PT302.

In above-described embodiment 11~25：The crosslinking agent is preferably glycerine and the mixture of pentaerythrite.

In above-described embodiment 11~25：The catalyst 2^#Preferably gasify what chemical product Co., Ltd provided for US Air Organic metal class compound products MB20, T-120 and T-125.

In above-described embodiment 11~25：Foamed time of the material at 60~90 DEG C is 17~24 seconds, gel time For 53~62 seconds, the not viscous time was 72~83 seconds.

In above-described embodiment 11~25：50 ± 1 ㎏ of apparent density/m of the obtained rigid foam³When, size (80 DEG C, 48h) of rate of change is 0.3% ± 0.04%, and compressive strength and bending strength are not less than 500KPa, and color is white.

In above-described embodiment：In used percentage, especially not dated, it is quality (weight) percentage, Described quality (weight) part can be gram or kilogram.

In above-described embodiment：The models such as technological parameter (temperature, time, concentration etc.) and each component numerical quantity in each step Any point enclosed is applicable.

The technology contents being not specifically delineated in present invention and above-described embodiment are compared with technology, the raw material Commercially available prod.

It can implement the invention is not restricted to above-described embodiment, described in present invention and there is the good result.

Claims

1. a kind of material for manufacturing rigid foam, it is characterized in that：The material is made up of component A and B component；

The component A is by the mass parts of high-functionality polyester polyol 80~120, catalyst 1^#0.5~0.7 mass parts, physics hair The mass parts of infusion 20~35, the mass parts of water 0.3~0.6, the mass parts of foam stabiliser 1~1.5 and the mass of crosslinking agent 4~6 Part mixing composition；

The B component is by the mass parts of isocyanates 84~126, catalyst 2^#0.1~0.3 mass parts mixing composition；

The high-functionality polyester polyol be average functionality be 2.8~3.0, viscosity be 7000~10000 at 25 DEG C MPaS, the mgKOH/g of hydroxyl value 380~450, the PEPA that acid number is 0.1~2 mgKOH/g；

The catalyst 1^#Be PT303, BX405, PT302, triethylene diamine, triethylamine, triethanolamine, diethylenetriamine and Mixture more than one or both of N, N- dimethyl cyclohexyl amine；Described PT303, BX405 and PT302 are US Air Gasify the aminated compounds product that chemical product Co., Ltd provides；

The physical blowing agent is one or both of pentamethylene, isopentane, HCFC-141b and HFC-245fa；HCFC- 141b, HFC-245fa are that the physical blowing agent product in China Chemical Industry market, production enterprise have：Zhejiang Juhua Stocks Trading Co. is limited Company, Jiangsu Bluestar Green Technology Co., Ltd., middleization blue sky Honeywell new material Co., Ltd；

The foam stabiliser is that the one or more and nucleation class in emulsification class organic silicon surfactant is organic One or more mixtures formed in silicon surface active agent；The emulsification class organic silicon surfactant is B- 84803rd, B-8534, AK8818, AK8811, AK8809, the nucleation class organic silicon surfactant are B-84805, B- 8545、SILBYK-9231、AK8882；Wherein：B-84803, B-8534, B-84805, B-8545 win for Germany creates industrial group Foam stabiliser product, SILBYK-9231 are German Bi Ke chemical companies foam stabiliser product, AK8818, AK 8882, AK 8811st, AK 8809 is that the foam stabiliser product in China Chemical Industry market, production enterprise have：Learn share in Mei Si Dehua, Jiangsu Co., Ltd；

The crosslinking agent is more than one or both of glycerine, pentaerythrite, trimethylolpropane, sorbierite and sucrose Mixture；

The isocyanates is the mixing of one or both of poly methylene poly phenyl poly isocyanate, toluene di-isocyanate(TDI) Thing；

The catalyst 2^#It is one or both of MB20, T-120, T-125, stannous octoate and dibutyl tin laurate Mixture above；Described MB20, T-120 and T-125 are the organic metal that US Air gasification chemical product Co., Ltd provides Class compound products.

2. the material of rigid foam is manufactured as described in claim 1, it is characterized in that：The high-functionality polyester polyol is The trade mark in China Chemical Industry market is PS-4027 PEPA product.

3. the material of rigid foam is manufactured as described in claim 1, it is characterized in that：The crosslinking agent is glycerine and season penta 4 The mixture of alcohol.

A kind of 4. preparation method of rigid foam, it is characterized in that step is：

A, component A is prepared：Take 80~120 mass parts high-functionality polyester polyols, 0.5~0.7 mass parts of catalyst 1^#, 20~ 35 mass parts physical blowing agents, 0.3~0.6 mass parts water, 1~1.5 mass parts foam stabiliser, 4~6 mass parts crosslinking agents, Component A batch can is placed in, high-speed stirred mixes 20~30 minutes, and component A is made, standby；

B, B component is prepared：Take the mass parts of isocyanates 84~126, catalyst 2^#0.1~0.3 mass parts, B component batch can is placed in, High-speed stirred mixes 20~30 minutes, and B component is made, standby；

The catalyst 2^#It is one or both of MB20, T-120, T-125, stannous octoate and dibutyl tin laurate Mixture above；Described MB20, T-120 and T-125 are the organic metal that US Air gasification chemical product Co., Ltd provides Class compound products；

C, rigid foam is prepared：Component A and B component are injected separately into foaming machine, high-speed stirred 15~40 seconds, control thing Material temperature degree is injected into inwall and scribbles releasing agent and be preheating to temperature as 60 under conditions of 25~30 DEG C, relative humidity ＜ 70% In~90 DEG C of mould, then the rigid foam of moulding by casting is put into 90~120 DEG C of baking ovens together with mould, dries 4 Room temperature is cooled to after~6 hours, opens mould, peels off and takes out white article, is obtained rigid foam.

5. the preparation method of the rigid foam as described in claim 4, it is characterized in that：High functionality gathers described in step a Ester polyol is the PEPA product that the trade mark in China Chemical Industry market is PS-4027.

6. the preparation method of the rigid foam as described in claim 4, it is characterized in that：Crosslinking agent described in step a is sweet The mixture of oil and pentaerythrite.