CN105440302A

CN105440302A - Polyurethane or isocyanurate composite plate and continuous production method thereof in production line

Info

Publication number: CN105440302A
Application number: CN201510262403.8A
Authority: CN
Inventors: 黄恒; 陈一民
Original assignee: Honeywell International Inc
Current assignee: Honeywell International Inc
Priority date: 2015-05-21
Filing date: 2015-05-21
Publication date: 2016-03-30
Also published as: WO2016184433A1

Abstract

The present invention provides a polyurethane or isocyanurate composite plate and a method for producing the polyurethane or isocyanurate composite plate in a continuous production line. According to the method disclosed by the present invention, by selecting components of a blowing agent composition, foam growth height accounts for at least 65%, preferably at least 75%, of the maximum free foaming height during touch panel time, so that anisotropy of the polyurethane composite plate production in the continuous production line is improved, particularly the compressive strength in a thickness direction and the proportion of the compressive strength in the thickness direction among overall compression strength in three directions are increased, and the dimensional stability of the polyurethane composite plate is improved.

Description

Urethane or poly-isocyanurate composition board and its tinuous production production method

Technical field

The present invention relates to urethane or poly-isocyanurate composition board technical field, specifically, the present invention relates to the better urethane of dimensional stability or poly-isocyanurate composition board that a kind of tinuous production produces and adopt tinuous production to produce the method for this kind of urethane or poly-isocyanurate composition board.

Background technology

Urethane (PUR) composition board generally comprises top layer, bottom and the foam layer between top layer and bottom.Rigid foam polyurethane is with low cost and have good insulation due to it, heat insulation, the advantages such as soundproof effect, therefore it is used widely in building material field.In view of for the higher standard of polyurethane composite plate fire performance and requirement, industry is tending towards the foam adopting polyurethane-modified polyisocyanurate foamed plastics (PIR), this is because it is not combustion-supporting, there is the fire performance that relatively common PUR is better.But, for the PUR produced by tinuous production, especially PIR, respectively to compressive strength skewness, particularly compressive strength is lower in a thickness direction, this causes Rigid foam polyurethane in life cycle, is tending towards shrinkage strain in a thickness direction under the effect of barometric point, makes its dimensional stability not good enough.

For PUR/PIR composition board, dimensional stability is very crucial performance, therefore for the PUR/PIR composition board that tinuous production is produced, needs badly and improve its dimensional stability, the resistance to compression especially on thickness direction.In the past, those skilled in the art had made following trial, comprising:

1) regulate reaction formula, such as, regulate polyvalent alcohol or polyol blends, silicon class tensio-active agent, catalyzer, the ratio shared by component such as whipping agent and other isocyanic ester;

2) change the design of composite plate structure, such as in China Patent Publication No. CN203222901U by adding reinforcing fiber to strengthen its ability of anti-deformation, improve its dimensional stability, extend its work-ing life thus;

3) increase the density of foam, as known in the art, larger foam density can obtain higher compressive strength, and can alleviate dimensional stability problems to a certain extent thus.

Although above solution alleviates dimensional stability problems to a certain extent, complicated operation, cost is higher or be unsuitable for tinuous production operation.

As for the whipping agent used in Rigid foam polyurethane continuous seepage, 141b and pentane are conventional pneumatogens.A kind of environment-friendly type premixed systems is disclosed in China Patent Publication No. CN102532456B, wherein pneumatogen is for comprising 365mfc/134a, and 365mfc accounts for the foaming agent composotion of 93% of mixture quality, its main purpose relates to environmental protection and does not relate to the improved performance of Rigid foam polyurethane in continuous lines production.

Summary of the invention

The object of the invention is to the compressive strength improving the urethane produced of tinuous production or poly-isocyanurate composition board, and then improve the dimensional stability of urethane or poly-isocyanurate composition board.

For realizing above object, according to an aspect of the present invention, provide a kind of urethane or poly-isocyanurate composition board, it at least comprises: top layer, bottom and the internal layer between described top layer and bottom, described internal layer is formed primarily of polyurethane foam or polyisocyanurate foam, wherein, described internal layer is produced by means of foaming agent composotion foaming by reactant on composite board continuous production line, and described foaming agent composotion component is arranged so that the growing height H of the foam of described internal layer in the touch panel time of the described top board of contact _tfree foaming height H maximum with it _maxratio be more than or equal to 65%, and be preferably more than or equal 75%.

Alternatively, in above-mentioned urethane or poly-isocyanurate composition board, described foaming agent composotion comprises component A and B component, and described component A is selected from by HFC-245fa, HFO-1233zd, HCFC-22, HCFC-142b, CO ₂, the group that HFC-227ea, HFC-134a form, and described B component is selected from by HCFC-141b, HFC-365mfc, 1336mzzm, Skellysolve A, pentamethylene, the group that iso-pentane forms.

Alternatively, in above-mentioned urethane or poly-isocyanurate composition board, the mass percent of described component A shared by described foaming agent composotion is greater than 20%, is preferably greater than 25%, is more preferably 25-75%, most preferably be 25-50%.

Alternatively, in above-mentioned urethane or poly-isocyanurate composition board, the oxygen index of described internal layer is greater than 23.

Alternatively, in above-mentioned urethane or poly-isocyanurate composition board, the compressive strength C of described internal layer on described thickness direction _xwith three-dimensional total compression intensity C _x+y+zratio be greater than 28%, be preferably more than 30%.

In urethane of the present invention or poly-isocyanurate composition board, polyurethane foam or polyisocyanurate foam pass through isocyanic ester, polyvalent alcohol or polyol blends, whipping agent, and other components such as catalyzer, activator and optional fire retardant, tinting material etc. are combined to prepare.Usually foam formulation is pre-blended into two portions.Isocyanic ester and optional various additive, the integral part A such as whipping agent, and, polyvalent alcohol and optional activator, catalyzer, the integral part B such as whipping agent, by reacting to produce polyurethane foam by part A and B injection plate in urethane or poly-isocyanurate composition board production process.Wherein, any organic multiple isocyanate all can be used for the synthesis of urethane or polyisocyanurate foam, preferably can be aromatic polyisocyanate.For polyvalent alcohol, can be polyester polyol, other examples comprise polyol.Aromatic polyester polyol can be used in the case of polyisocyanurate foam.

According to a further aspect in the invention, provide a kind of method adopting tinuous production to produce urethane or poly-isocyanurate composition board, described urethane or poly-isocyanurate composition board at least comprise top layer, bottom and the internal layer between described top layer and bottom, described internal layer is formed primarily of polyurethane foam or polyisocyanurate foam, wherein, described method is included on composite board continuous production line and adopts foaming agent composotion to make reactant foaming produce described internal layer, arranging described foaming agent composotion component makes the foam of described internal layer at the growing height H of touch panel time of the described top board of contact _tfree foaming height H maximum with it _maxratio be more than or equal to 65%, and be preferably more than or equal 75%.

Alternatively, in the above-mentioned methods, described foaming agent composotion comprises component A and B component, and described component A is selected from by HFC-245fa, HFO-1233zd, HCFC-22, HCFC-142b, CO ₂, the group that HFC-227ea, HFC-134a form, and described B component is selected from by HCFC-141b, HFC-365mfc, 1336mzzm, Skellysolve A, pentamethylene, the group that iso-pentane forms.

Alternatively, in the above-mentioned methods, the mass percent of described component A shared by described foaming agent composotion is greater than 20%, is preferably greater than 25%, more preferably 25-75%, most preferably is 25-50%.

Alternatively, in the above-mentioned methods, described foaming agent composotion is made up of component A and B component, and described component A is HFC-245fa and described B component is HCFC-141b, or described component A is HFO-1233zd and described B component is pentamethylene, Skellysolve A or iso-pentane.

Alternatively, in the above-mentioned methods, the mass percent of described component A in described foaming agent composotion is at 25-50%.

Alternatively, in the above-mentioned methods, described foaming agent composotion is made up of component A and B component, and described component A is HFC-245fa and described B component is HCFC-141b, and the mass percent of described component A in described foaming agent composotion is at 25-38%.

Alternatively, in the above-mentioned methods, the oxygen index of described internal layer is greater than 23.

In accordance with a further aspect of the present invention, provide a kind of method adopting tinuous production to produce urethane or poly-isocyanurate composition board, described urethane or poly-isocyanurate composition board at least comprise top layer, bottom and the internal layer between described top layer and bottom, described internal layer is formed primarily of polyurethane foam or polyisocyanurate foam, wherein, described method is included on composite board continuous production line and adopts foaming agent composotion to make reactant foaming produce described internal layer, described foaming agent composotion component is set, and adjust described reaction volume, described composite board continuous production line speed, make the foam of described internal layer at the growing height H of touch panel time of the described top board of contact _tfree foaming height H maximum with it _maxratio be more than or equal to 65%, and be preferably more than or equal 75%.

Alternatively, in the above-mentioned methods, also comprise and regulate reactant to inject density, make the foam of described internal layer at the growing height H of touch panel time of the described top board of contact _tfree foaming height H maximum with it _maxratio be more than or equal to 65%, and be preferably more than or equal 75%.

In addition, in above urethane or poly-isocyanurate composition board or urethane or poly-isocyanurate composition board production method, described foaming agent composotion can comprise component A and B component, described component A is selected from by HFC-245fa, HFO-1233zd, HCFC-22, HCFC-142b, CO ₂, the group that HFC-227ea, HFC-134a form, and described B component is selected from by HCFC-141b, HFC-365mfc, 1336mzzm, Skellysolve A, pentamethylene, the group that iso-pentane forms, the weight percent of described component A in described foaming agent composotion can be: >20%; Or 20-80%, or 20-75%, or 20-50%; Or >25%; Or 25-80%, or 25-75%, or 25-50%, or 25-38%.

In addition, in above urethane or poly-isocyanurate composition board or urethane or poly-isocyanurate composition board production method, the foam of described internal layer is at the growing height H of the touch panel time of the described top board of contact _tfree foaming height H maximum with it _maxratio for being more than or equal to 65%, and be preferably more than or equal 75%; Alternatively, and be less than or equal to 95% or 90%.。

In the method for the invention, foaming agent composotion refers to pneumatogen.Usually, in the production of polyurethane foam or polyisocyanurate foam, also can comprise and add water as chemical foaming agent.

Tinuous production of the present invention produces the method for urethane or polycyanurate composition board, comprises HFC-245fa, HFO-1233zd, HCFC-22, HCFC-142b, CO by adding ₂hFC-227ea, or the component A of HFC-134a and combination thereof, as mixed foaming agent, be particularly useful for original in comprising HCFC-141b, HFC-365mfc, 1336mzzm, Skellysolve A, pentamethylene, the production of the urethane that the B component of iso-pentane is prepared as foaming agent foam or polycyanurate foam, thus significantly improve the distribution of its three-dimensional compressive strength, the especially compressive strength of thickness direction.

In addition, in this article, term " free foaming " refers to foam free growth when not limiting (compacting), swells, until foaming process terminates; Term " maximum free foaming height " refers to reactant accessible maximum height under " free foaming " condition; Term " touch panel time " refers to the time of reactant contact top layer on tinuous production; Wire drawing time or gel time refer to that reactant is transformed into the time of solid gel.

In addition, in this article, dimensional stability is according to GB/T8811-2008 standard testing; Compressive strength is according to GB/T8813-2008 standard testing; Oxygen index is according to GB/T2406-2008 standard testing; Density is according to GB/T6343-2009 standard testing; Thermal conductivity is according to GB/T10294-2008 standard testing.

Benefit of the present invention is at least following:

1) during formation of foam, the ratio accounting for free foaming height at the height of touch panel time (time point of foam contacting top layer) front foam rising is larger, then abscess is more tending towards isotropy, this is conducive to the total compression intensity improving Rigid foam polyurethane, the compressive strength especially on thickness direction.Compressive strength evenly distribution, and on thickness direction the increase of compressive strength make the compressive strength of thickness direction account for three-dimensional total compression intensity ratio increase.In addition isotropic foam is also favourable for avoiding foam cell to be out of shape.To sum up, the dimensional stability of Rigid foam polyurethane improves.

2) even if a small amount of foam layer mean density reducing composition board also can obtain better compressive strength.

3) higher foam rises and can reduce the possibility of the foam rollover phenomenon that bubble may be caused to produce.

4) foam rises particularly useful on polyurethane foam composite board continuous production line faster, especially for the high-speed production lines of PIR slab (>100mm).

5) the bubble growth height of higher rate can reduce foam pressure in a mold, and demould time is reduced, and can improve line speed, increase production efficiency further.

Accompanying drawing explanation

Hereafter will describe specific embodiments of the invention by reference to the accompanying drawings, in the drawings:

Fig. 1 shows reactant lifting height and the relation of time in PUR system and PIR system;

Fig. 2 shows the abscess of foam orientation possible in cube mold;

Fig. 3 shows the schematic diagram of Rigid foam polyurethane tinuous production;

Fig. 4 shows the possible orientation of abscess in Rigid foam polyurethane in tinuous production;

Fig. 5 shows all directions and the production line direction of urethane compound version in tinuous production;

Under Fig. 6 shows identical feed situation, the graph of a relation between the reaction times of 141b blowing agent system and 141b/245fa blowing agent combination objects system and aspect ratio (i.e. the ratio of growing height and maximum free foaming height);

Fig. 7 show the touch panel time identical when, the reaction times of 141b whipping agent and 141b/245fa foaming agent composotion and the graph of a relation of growing height;

Fig. 8 shows the schematic diagram of laboratory simulation mould;

Fig. 9 shows in 141b/245fa blowing agent combination objects system, and under different 245fa content, during the touch panel time, growing height accounts for the ratio of maximum free foaming height; And

Figure 10 shows in HFO-1233zd/ pentamethylene blowing agent combination objects system, and under various HF O-1233zd content, during the touch panel time, growing height accounts for the ratio of maximum free foaming height.

embodiment:

about the principal reaction in foaming process

…(1)

…(2)

…(3)

Main in polyurethane foam production process exist three kinds of reactions, is respectively: polyvalent alcohol and isocyanic ester generate the reaction (1) of polyurethanyl group, react also referred to as PUR; Isocyanic ester and water generate polyureas group and CO ₂reaction (2), a large amount of heat release of this reaction, and pneumatogen is gasified, makes reaction liquid expand, and this phenomenon is in the industry also referred to as " milky white or inspire "; And the trimerization reaction (3) between isocyanic ester is to produce poly-isocyanurate group, reacts also referred to as PIR.

-NCO and the ratio of-OH are set to 1.0 to guarantee that isocyanic ester reacts with polynary alcohol and water completely in producing by common PUR composition board usually.Improving to make composition board resistivity against fire for obtaining more poly-isocyanurate group, usually-NCO and the ratio of-OH being arranged to 1.5-4.0, making to leave more-NCO group to participate in trimerization reaction.PIR reaction makes foam have better fire performance and compressive strength.In addition, due to a large amount of isocyanic ester of water consumption, therefore usually control at lower level by water-content in PIR system, this makes PIR system mid-early stage sluggish, and the later stage suddenly grows.

Figure 1 illustrates the schematic diagram reacting lifting height and time in PUR system and PIR system, wherein dotted line shows gel time or wire drawing time.As shown in the figure, as mentioned previously, due to PIR system sluggish in early stage, the later stage suddenly grows, therefore the lifting height in PIR system when same time (example gel time) is less than PUR system, as hereinbefore set forth, this makes in PIR system, on tinuous production during production composition board, thickness direction compressive strength and dimensional stability problems thus more outstanding.

the relation of foam cell orientation and compressive strength

With reference to figure 2, wherein mould is without upper cover, and for free growing polyurethane foam, in abscess formation and process of growth, foam structure is roughly elliposoidal.Because abscess is subject to the impact of two side molds, therefore abscess becomes elliposoidal (because its both sides are restricted main upwards growth) substantially before contact top board, as shown in Figure 2, its primary growth direction is along arrow D, therefore the long axis thickness direction X of oval shaped cells 2.

Verified, for elliposoidal abscess, compressive strength maximum (compressive strength can be measured according to GB/T8813-2008) on its long axis direction.Maybe can infer, the direction of greatest compressive strength is abscess long axis direction, therefore merits attention, and the method it is conceivable that the compressive strength strengthened on thickness direction can be the quantity or ratio that improve machine-direction oriented abscess.

produce about continuous lines

With reference to figure 3, it illustrates the schematic diagram of Rigid foam polyurethane production line.Wherein top layer 32 is supported by some supporting rolls 31, and bottom 33 is laid on scene, by transport unit driven synchronous with bottom 33 of top layer 31 and to right direction translation in figure, by laminating roll 34.Reactant 35 is not stopped to flow between top layer and bottom by foaming machine sparger 36, T as shown in the figure ₂for reactant growth and contact the time point of top layer 31, also become touch panel time or touch panel time point herein, T ₁for gel time point.

When producing continuously line and producing, the lamination effect of top layer and reactant are expanded and occurs simultaneously.Liquid starting material injects on the bottom surface of composition board, and each reaction occurs successively or simultaneously, and heat produces and makes expansion of liquids increase until its contact top layer.Generally speaking, for concrete reactant composition, gel time or the wire drawing time of reactant are fixing.Production practice prove, time point (touch panel time) the best that reactant grows to contact top layer is in a thickness direction at its gel time first 5 seconds, namely makes T ₁-T ₂=5s.After foam touches top, continuation is also expanded by reactant, until reaction terminates, and whole foam layer sclerosis.

With reference to figure 4 and Fig. 5, wherein Fig. 4 shows the possible microtexture of Rigid foam polyurethane internal layer that tinuous production is produced, and Fig. 5 shows all directions of composition board.Wherein, herein and herein, M direction or Y-direction are production line traffic direction, and X is thickness direction, and Z is width.

Can find in compressive strength test, in the Rigid foam polyurethane that ordinary skill continuous lines is produced, on different directions, compressive strength differs greatly.Specifically, in an example, X-direction, namely thickness direction intensity is C _x=92kPa, Z-direction and width are C _z=98kPa, Y-direction, namely machine direction or pressing direction intensity are C _y=221kPa.The reasonable dismissal of above compressive strength distribution is, the long axis direction of abscess substantially along Y-direction, in other words in abscess the quantity of long axis Y-direction orientation or probability higher.The reasonable guess of the reason of this situation is: 1) after reactant touches top, it is at X, the growth of Z-direction is subject to the restriction of laminating roll and side guard, its free growing direction of unique permission is Y-direction, therefore the growth before touch panel time extremely completely solidification is substantially along Y-direction, thus make abscess long axis Y-direction orientation.Therefore As described in detail below, in this stage, the expansion namely between the touch panel time to gel time is unfavorable for X-direction compressive strength; 2) on production line traffic direction, the liquid more early injected more early solidifies and hardens, and the liquid of rear injection cannot flow to this direction, is tending towards the opposite direction growth run along production line after making reactant touch panel.Therefore the continuous Rigid foam polyurethane that line is produced that produces is tending towards having the compressive strength in larger Y-direction, and at X, in Z-direction, compressive strength is less.But, when X-direction intensity is lower than barometric point, be easy to the situation that composition board shrinkage strain occurs.

blowing agent system compares with HCFC-141b+HFC-245fa blowing agent system

As shown in Figure 6, when not considering to touch top, for the condition freely risen, under it illustrates identical feed situation, HCFC-141b (be called for short 141b) whipping agent and 141b are mixed into reaction times that certain proportion HFC-245fa (being called for short 245fa) whipping agent (hereinafter referred to as 141b/245fa system) contrasts and aspect ratio (wherein aspect ratio are actual growing height and maximum free foaming height H _maxratio) graph of a relation.Present definition foam is free growth when not limiting (compacting), swells, until accessible maximum height is maximum free foaming height H at the end of foaming process _max.Experiment proves, when being mixed into 245fa with certain proportion, setting gel time or the point of first 5 seconds of wire drawing time are T point, and at T point place, 141b+245fa whipping agent is significantly higher than the growing height of 141b whipping agent.

Especially, as hereafter proved by experiment, at the growing height H of touch panel time _twith maximum free foaming height H _maxratio be more than or equal to 65%, when being more preferably more than or equal to 75%, the distribution of foam layer compressive strength in three directions can be made more reasonable, make foam layer do not sacrifice or not other directional performances of materially affect prerequisite under, increase the compressive strength of thickness direction, improve its dimensional stability, the dimensional stability especially on thickness direction.

For ease of understanding, with reference to figure 7, owing to using in the system of 141b+245fa whipping agent, reactant growth is faster, therefore for the same touch panel time, 141b/245fa system can reduce feeding coal also can reach the lifting height identical with 141b system.Therefore for realizing the identical tactile top time, use the system of 141b+245fa whipping agent, can reduce on a small quantity reaction volume (when substantially not substantial effect finished foam layer density).Under such prerequisite, can know and see, 141b/245fa whipping agent is at touch panel time T ₂after upwards expansion height H1 be less than H2 in 141b system, as produced in continuous lines, behind tactile top, 141b system can be more along the growth of Y-direction, thus the quantity of abscess long axis Y-direction orientation or ratio are increased.Therefore compared to independent 141b system, keep that the abscess of X orientation is more or probability is higher in 141b/245fa system, therefore X-direction intensity is also larger.

laboratory experiment

Applicant attempts the continuous flow procedure simulating the polyurethane foam board adopting different blowing agent system in the lab.As shown in Figure 8, foam foams usually in hexahedral cube mold or container.Polyvalent alcohol and isocyanic ester mixed reactant and other auxiliary components are injected container, and liquid expands to all directions, and contacts end face, is solidified into solid foam subsequently.

For simulating tinuous production in the lab, provide cube mold ABCDEFGH, wherein ACGE side keeps opening wide, and after foam touches top, it is tending towards flowing to ACGE direction under the effect of enough pressure.Specifically, first, ACDB side and ACGE side are opened wide, and inject a certain amount of each group reaction thing, should be noted, the composition of each group reaction objects system makes gel time identical through fine setting, and the touch panel time is set to gel time first 5 seconds.Subsequently, ACDB side seal closed and makes ACGE side keep opening wide, carrying out foamable reaction, and finished product is tested.

experiment 1:141b system and 141b/245fa system

Formula and reactant

Table 1 is filled a prescription

Component	Title	1#	2#	3#	4#
						GR 835G	Sucrose based polyether polyols	50	50	50	50
PS2412	Polyester polyol	50	50	50	50
						TCPP	Fire retardant	16	16	16	16
PC5	Amine catalyst	0.3	0.3	0.3	0.3
						K15	Metal catalyst	1.50	1.60	1.65	1.85
DC193	Activator	2.0	2.0	2.0	2.0
						Water		1.0	1.0	1.0	1.0
141b	Blowing agent composition A	24.0	18.6	12.8	6.6
						245fa	Blowing agent composition B		6.2	12.8	19.9
PMDI	BASF M20S	210	210	210	210

Utilize the 245fa of basic significant proportion to substitute 141b in four group of formula, account for percent 0 of total whipping agent ratio respectively, 25,50,75, be respectively sample 1#, 2#, 3# and 4#.In addition, the weight of whipping agent gross weight and catalyzer has done fine setting to obtain close wire drawing time and core or internal layer density.

Table 2245fa ratio/wire drawing time/core density

	1#	2#	3#	4#
					The mass percent of 245fa in whipping agent	0	25	50	75
The wire drawing time	77	79	76	77
					Core density	36.6	36.4	36.6	36.8

As shown in Figure 9, instrument FOAMAT is used to test 245fa proportion and bubble growth aspect ratio (i.e. bubble growth height H and maximum free foaming height H in foaming agent composotion _maxratio H/H _max) relation, wherein touch panel time T ₂, i.e. the gel time growing height H of first 5 seconds _tmarked, as shown in the figure when being mixed into the 245fa of 25%, reactant is at the growing height of touch panel time point and the ratio of maximum free foaming height and H _t/ H _maxbe 65%, and increase with 245fa content, at the growing height of touch panel time point than raising further with the ratio of maximum free foaming height.

The compressive strength of each sample of table 3

	1#	2#	3#	4#
					Overall consistency kg/m ³	54.5	51.8	47.7	46.4
Core density kg/m ³	40.6	39.2	38.8	38.5
					X-direction compressive strength kPa	98	135	148	142
Y-direction compressive strength kPa	188	159	151	148
					Z-direction compressive strength kPa	91	94	97	106

Experiment proves, even if having lower injection density and core density, 245fa/141b system still has good X-direction compressive strength, and this characteristic produces characteristic quite crucial for Rigid foam polyurethane for tinuous production.

Table 4 three-dimensional total compression intensity and thickness direction compressive strength account for the ratio of total compression intensity

	1#	2#	3#	4#
					245fa proportion in whipping agent	0%	25%	50%	75%
Total compression intensity	377 kPa	388 kPa	396 kPa	396 kPa
					Thickness direction compressive strength accounts for the ratio of total compression intensity	26%	35%	37%	36%

As seen from Table 4, total add the compressive strength that a certain amount of 245fa whipping agent makes to increase (even if foam density minimizing) in existing 141b whipping agent.And when foaming agent composotion, the compressive strength on thickness direction, and its in three-dimensional total compression intensity, (namely X is to the compressive strength C of+Y-direction+Z-direction _x+y+z) in shared ratio be obtained for increase, the compressive strength of finished foam plate is more evenly distributed rationally, although Y-direction there is a small amount of minimizing, it can not produce adverse influence.Therefore the anisotropy of Rigid foam polyurethane effectively can be improved by the present invention, the compressive strength on thickness direction is improved, to strengthen its dimensional stability.

Table 5 lattice specimen size stability

	1#	2#	3#	4#
					The ratio of 245fa in whipping agent (%)	0	25	50	75
Size changing rate (%) under the same terms	6.80	2.55	2.21	2.83

Dimensional stability can according to GB/T8811-2008 standard testing, and experiment condition is 70 degrees Celsius, places the size changing rate of 24 hours samples under the humidity of 95%.From then on table visible shared by 245fa ratio be greater than 25%, when being preferably 50%, dimensional stability is better.

experiment 2: pentamethylene and pentamethylene/HFO-1233zd system

Similar experiment can perform equally between cyclopentane systems and pentamethylene/HFO-1233zd (hereafter for Solstice LBA1233zd) system, is below experimental result.

Formula and reactant

Table 6 is filled a prescription

Component	Title	1#	2#	3#	4#
						GR 835G	Sucrose based polyether polyols	50	50	50	50
PS2412	Polyester polyol	50	50	50	50
						TCPP	Fire retardant	16	16	16	16
PC5	Amine catalyst	0.3	0.3	0.3	0.3
						K15	Metal catalyst	1.60	1.70	1.85	2.05
DC193	Activator	2.0	2.0	2.0	2.0
						Water		1.0	1.0	1.0	1.0
Pentamethylene	Blowing agent composition A	15	12.7	9.8	5.7
						HFO-1233zd	Blowing agent composition B		4.3	9.8	17.2
PMDI	BASF M20S	210	210	210	210

Utilize the HFO-1233zd displaced loop pentane of basic significant proportion in four group of formula, account for percent 0 of total whipping agent ratio respectively, 25,50,75, be respectively sample 1#, 2#, 3# and 4#.In like manner, the weight of whipping agent and catalyzer has done fine setting to obtain close wire drawing time and core density.

Table 7HFO-1233zd ratio/wire drawing time/core density

	1#	2#	3#	4#
					The mass percent of HFO-1233zd in whipping agent	0	25	50	75
The wire drawing time	75	78	77	77
					Core density	34.8	35.4	35.7	5.8

As shown in Figure 10, instrument FOAMAT is used to test HFO-1233zd proportion and bubble growth aspect ratio (i.e. bubble growth height H and maximum free foaming height H in foaming agent composotion _maxratio H/H _max) relation, wherein touch panel time, i.e. the gel time growing height H of first 5 seconds _tmarked, as shown in the figure when being mixed into the HFO-1233zd of 25%, reactant is at the growing height of touch panel time point and the ratio of maximum free foaming height and H _t/ H _maxbe 65%, and increase with 245fa content, at the growing height of touch panel time point than raising further with the ratio of maximum free foaming height.

The compressive strength of each sample of table 8

	1#	2#	3#	4#
					Overall consistency kg/m ³	56.8	53.7	49.4	48.2
Core density kg/m ³	42.4	42.1	41.8	39.3
					X-direction compressive strength kPa	77	152	179	156
Y-direction compressive strength kPa	233	221	215	208
					Z-direction compressive strength kPa	163	153	152	136

Experiment proves, even if having lower injection density and core density, HFO-1233zd/ cyclopentane systems still has good X-direction compressive strength.

Table 9 three-dimensional total compression intensity and thickness direction compressive strength account for the ratio of total compression intensity

	1#	2#	3#	4#
					HFO-1233zd proportion in whipping agent	0%	25%	50%	75%
Total compression intensity	473	527	546	500
					Thickness direction compressive strength accounts for the ratio of total compression intensity	16.6	28.9	32.8	31.2

As seen from Table 9, total add the compressive strength that a certain amount of HFO-1233zd whipping agent makes to increase (even if foam density reduces on a small quantity) in existing pentamethylene whipping agent.And when foaming agent composotion, compressive strength on thickness direction, and its ratio shared in total compression intensity is obtained for increase, the compressive strength of finished foam plate is more evenly distributed rationally, although Y-direction there is a small amount of minimizing, it can not produce adverse influence.Therefore the anisotropy of Rigid foam polyurethane effectively can be improved by the present invention, the compressive strength on thickness direction is improved, to strengthen its dimensional stability.

The each specimen size stability of table 10

	1#	2#	3#	4#
					The ratio of HFO-1233zd in whipping agent	0	25	50	75
Size changing rate under the same terms	10.7	3.58	2.87	3.05

Dimensional stability can according to GB/T8811-2008 standard testing, and experiment condition is 70 degrees Celsius, under the humidity of 95%, place 24 hours its size changing rates.From then on table visible shared by HFO-1233zd ratio be greater than 25%, be preferably dimensional stability about 50% time better.

conclusion

Be to be understood that, those skilled in the art can carry out various change to Blowing agent composition under above-mentioned experiment inspires, when calculating ratio shared by each whipping agent and touch panel time in mixture by test method of the present invention reactant growing height and maximum can relation between free growth height, and select suitable foaming agent composotion to realize identical technical purpose.In any case the conclusion that applicant obtains in revision test is the component arranging foaming agent composotion, as long as reactant growing height H when making the touch panel time _twith maximum can free growth height H _maxbetween ratio H _t/ H _maxbe greater than 65%, the remarkable improvement of thickness direction compressive strength when being more preferably greater than 75%, can be realized.

Should be appreciated that experimental technique disclosed in this invention can repeat to be implemented on various blowing agent combination, to obtain corresponding experimental result.Applicant proves that following foaming agent composotion component is preferred by experiment, and wherein whipping agent comprises component A and B component, and wherein the alternate example of component A includes but not limited to: HFC-245fa, HFO-1233zd, HCFC-22, HCFC-142b, CO ₂, HFC-227ea, HFC-134a; The alternate example of B component includes but not limited to HCFC-141b, HFC-365mfc, 1336mzzm, Skellysolve A, pentamethylene, iso-pentane.That is, using the combination of any above component A and B of suitable proportion as foaming agent composotion, make the reactant of described internal layer at the growing height H of touch panel time _tfree foaming height H maximum with it _maxratio be more than or equal to 65%, and be preferably more than or equal 75%, then effective improvement of thickness direction dimensional stability all can be provided.For all combinations, can find that after experimental study the mass percent of component A in foaming agent composotion is more than 20%, preferred 20%-75%, more preferably respectively more satisfactory to compressive strength distribution during 20%-50%.Dimensional stability is also better.Therefore can with reference to above ratio setting blowing agent component for the foaming agent composotion without experimental demonstration.

Should be appreciated that for tinuous production, by regulating reaction volume, reactant injects density, and one in line speed or more makes reactant fully grow before the touch panel time, thus reaches the growing height H of touch panel time _tfree foaming height H maximum with it _maxratio be more than or equal to 65%, and be preferably more than or equal 75% object.And reaction volume, reactant injects density, and the selection of line speed is based on realizing identical touch panel time this purpose.Specifically, after room test obtains the preferred version of foaming agent composotion component by experiment, by regulating reaction volume, produce linear velocity, reactant injects the parameters such as density and obtains the close touch panel time, and makes the growing height H when the touch panel time _tfree foaming height H maximum with it _maxratio be more than or equal to 65%, and be preferably more than or equal 75% object.Applicant surprisingly finds, when foaming agent composotion, even if reduce reaction volume, increase product linear velocity also can obtain the compressive strength on larger thickness direction.

Should be appreciated that the top layer of the composition board in the present invention and bottom can be made up of material conventional in any this area, but be more suitable for top layer of the present invention and primer includes but not limited to, steel, aluminium, paper or glued board.In addition, for internal layer, the refractory materials that the oxygen index that the present invention is more suitable for internal layer is greater than 23.In addition, water uses as chemical foaming agent in above-mentioned various formula, promotes foaming process.

In addition, when selecting Blowing agent composition, also should consider that the compressive strength in other directions can not be subject to substantial effect when improving thickness direction compressive strength.Although desired during the compressive strength of thickness direction, it should be noted that visible ratio and the C accounting for three-dimensional total compression intensity at thickness direction in experiment _x/ C _x+y+zmore than 28%, preferably more than 30% time, respectively to dimensional stability be tending towards reasonable, like this anisotropy is significantly improved.And whipping agent according to the present invention also may come from foaming for the improvement of dimensional stability during the reason such as release or internal pressure release of more internal stresss.

Should be appreciated that specific embodiment described above only in order to more clearly describe the principle of this patent, wherein all parts being specialized and principle of the present invention is easier to understand.Without departing from the scope of the invention, those skilled in the art easily can carry out various amendment to the present invention.Therefore should be understood that, scope of the present invention should not limited by above specific embodiment.

Claims

1. a urethane or poly-isocyanurate composition board, it at least comprises: top layer, bottom and the internal layer between described top layer and bottom, described internal layer is formed primarily of polyurethane foam or polyisocyanurate foam, it is characterized in that, described internal layer is produced by means of foaming agent composotion foaming by reactant on composite board continuous production line, and described foaming agent composotion component is arranged so that the growing height H of the foam of described internal layer in the touch panel time of the described top board of contact _tfree foaming height H maximum with it _maxratio be more than or equal to 65%, and be preferably more than or equal 75%.

2. urethane according to claim 1 or poly-isocyanurate composition board, is characterized in that, described foaming agent composotion comprises component A and B component, and described component A is selected from by HFC-245fa, HFO-1233zd, HCFC-22, HCFC-142b, CO ₂, the group that HFC-227ea, HFC-134a form, and described B component is selected from by HCFC-141b, HFC-365mfc, 1336mzzm, Skellysolve A, pentamethylene, the group that iso-pentane forms.

3. urethane according to claim 2 or poly-isocyanurate composition board, is characterized in that, the mass percent of described component A shared by described foaming agent composotion is greater than 20%, is preferably greater than 25%, is more preferably 25-75%, most preferably be 25-50%.

4. urethane according to claim 1 or poly-isocyanurate composition board, is characterized in that, the oxygen index of described internal layer is greater than 23.

5. urethane according to claim 1 or poly-isocyanurate composition board, is characterized in that, the compressive strength C of described internal layer on described thickness direction _xwith three-dimensional total compression intensity C _x+y+zratio be greater than 28%, be preferably more than 30%.

6. the method adopting tinuous production to produce urethane or poly-isocyanurate composition board, described urethane or poly-isocyanurate composition board at least comprise top layer, bottom and the internal layer between described top layer and bottom, described internal layer is formed primarily of polyurethane foam or polyisocyanurate foam, it is characterized in that, described method is included on composite board continuous production line and adopts foaming agent composotion to make reactant foaming produce described internal layer, arranging described foaming agent composotion component makes the foam of described internal layer at the growing height H of touch panel time of the described top board of contact _tfree foaming height H maximum with it _maxratio be more than or equal to 65%, and be preferably more than or equal 75%.

7. method according to claim 6, is characterized in that, described foaming agent composotion comprises component A and B component, and described component A is selected from by HFC-245fa, HFO-1233zd, HCFC-22, HCFC-142b, CO ₂, the group that HFC-227ea, HFC-134a form, and described B component is selected from by HCFC-141b, HFC-365mfc, 1336mzzm, Skellysolve A, pentamethylene, the group that iso-pentane forms.

8. method according to claim 7, is characterized in that, the mass percent of described component A shared by described foaming agent composotion is greater than 20%, is preferably greater than 25%, more preferably 25-75%, most preferably is 25-50%.

9. method according to claim 7, it is characterized in that, described foaming agent composotion is made up of component A and B component, and described component A is HFC-245fa and described B component is HCFC-141b, or described component A is HFO-1233zd and described B component is pentamethylene, Skellysolve A or iso-pentane.

10. method according to claim 9, is characterized in that, the mass percent of described component A in described foaming agent composotion is at 25-50%.

11. methods according to claim 6, is characterized in that, the oxygen index of described internal layer is greater than 23.