Polymerized MDI with low halogenated alicyclic hydrocarbon substance content as well as preparation method and application thereof

Abstract

According to the polymeric MDI with the low halogenated alicyclic hydrocarbon content and the preparation method and application thereof, the polymeric MDI with the low halogenated alicyclic hydrocarbon content is applied to a polyurethane adhesive, and the opening time of the polyurethane adhesive can be prolonged. According to the polymerized MDI with the low halogenated alicyclic hydrocarbon substance content, the halogenated alicyclic hydrocarbon substance content in the polymerized MDI is smaller than or equal to 15 ppm, preferably smaller than or equal to 10 ppm, more preferably smaller than or equal to 5 ppm, and further preferably smaller than or equal to 1 ppm.

Description

Technical Field

[0001] The invention relates to the technical field of polymerized MDI, and in particular to a polymerized MDI with low halogenated aliphatic cyclic hydrocarbon content, and a preparation method and application thereof. Background Art

[0002] Polymethylene polyphenyl polyisocyanate is one of the important raw materials for preparing polyurethane, mainly used for producing polyurethane rigid foam, and is applied to the fields of household appliances, cold storage, containers, building insulation materials, etc. As is well known, the current production method generally comprises the following steps: firstly, aniline and formaldehyde are subjected to a condensation reaction under an acid catalyst to generate DAM (a mixture of diaminodiphenylmethane and polyphenyl polymethylene polyamines, referred to as polyamines), and DAM is subjected to a liquid phase phosgenation reaction with phosgene in a solvent under an inert solvent environment to obtain a reaction mixture, and the reaction mixture is subjected to phosgene removal, hydrogen chloride stripping, solvent removal, and refined separation to obtain the corresponding pure MDI (diphenylmethane series diisocyanates) and polymeric MDI products (a mixture of diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates).

[0003] The method disclosed in the current patent is mainly to remove the phenyl isocyanate impurities (PI) in the polymerized MDI product. Many control schemes have been proposed in the art for reducing the PI content. For example, patent application CN114044746A proposes that by adding a special catalyst during the alkali neutralization process of the DAM reaction solution, the PI precursor impurity content in the DAM finally prepared can be reduced, thereby obtaining isocyanates of low PI substances. Patent application CN113474388A proposes to add a PI self-polymerization catalyst to the circulating solvent, catalyze the self-polymerization of PI in the solvent to generate carbodiimide, and the carbodiimide reacts with the MDI in the system to generate uretonimine, which eventually enters the product and does not affect the product performance. In addition, in order to avoid the catalyst from circulating into the system to catalyze the self-polymerization of MDI, a terminator needs to be added to deactivate the catalyst before the solvent is reused. Patent US4405527 describes the purpose of reducing the PI content of the system by reacting the PI in the solvent with a stoichiometric excess of polyamines or diols to convert them into carbamates or ureas.

[0004] The current methods for improving the quality of polymerized MDI products in the art often require the introduction of new materials into the system, which increases operating costs and also brings new impurities, which is prone to new pollution; secondly, changes to the original process will inevitably bring other adverse effects that are difficult to evaluate. In addition, none of the above-mentioned prior arts involve the control of halogenated alicyclic hydrocarbon impurities in polymerized MDI, nor do they realize the impact of halogenated alicyclic hydrocarbon impurities on the open time of polymerized MDI when used in the field of polyurethane adhesives (such as potting glue). Summary of the invention

[0005] The present invention provides a polymeric MDI with low halogenated alicyclic hydrocarbon content, a preparation method and application thereof. The present invention provides a polymeric MDI with controlled halogenated alicyclic hydrocarbon content, which is applied to polyurethane adhesives to improve the open time of polyurethane adhesives.

[0006] To achieve the purpose, the present invention provides the following technical solutions:

[0007] In one aspect, the present invention provides a polymeric MDI having a low content of halogenated alicyclic hydrocarbon substances, wherein the content of halogenated alicyclic hydrocarbon substances in the polymeric MDI is ≤15 ppm, preferably ≤10 ppm, more preferably ≤5 ppm, and further preferably ≤1 ppm.

[0008] The content of halogenated aliphatic cyclic hydrocarbon substances in the polymeric MDI is, for example, 0-15ppm, for example, 0ppm, 0.05ppm, 0.1ppm, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, 11ppm, 12ppm, 13ppm, 14ppm or 15ppm, etc.; preferably 0-10ppm; more preferably 0-5ppm; further preferably 0-1ppm, for example 0ppm, 0.0001ppm, 0.001ppm, 0.01ppm, 0.05ppm, 0.1ppm, 0.3ppm, 0.5ppm, 0.7ppm, 1ppm, etc.

[0009] In some embodiments, the content of halogenated alicyclic hydrocarbon substances in the polymeric MDI is >0 and ≤15ppm, such as 0.0001-15ppm, 0.01-15ppm, 0.1-15ppm, 0.5-15ppm, etc. In some embodiments, the content of halogenated alicyclic hydrocarbon substances in the polymeric MDI is >0 and ≤10ppm, such as 0.0001-10ppm, 0.01-10ppm, 0.1-10ppm, 0.5-10ppm, etc. In some embodiments, the content of halogenated alicyclic hydrocarbon substances in the polymeric MDI is >0 and ≤5ppm, such as 0.0001-5ppm, 0.01-5ppm, 0.1-5ppm, 0.5-5ppm, etc. In some embodiments, the content of halogenated alicyclic hydrocarbon substances in the polymeric MDI is >0 and ≤1ppm, such as 0.0001-1ppm, 0.01-1ppm, 0.1-1ppm, 0.5-1ppm, etc.

[0010] Furthermore, the halogenated aliphatic cyclic hydrocarbon substance is one or more compounds having the following structural formulas (I) and (II):

[0011]

[0012] Wherein, each R in the structural formula (I) and (II) is independently hydrogen, methyl, halomethyl or halogen, and at least one of the R in the structural formula (I) and (II) is halogen or halomethyl; that is, the halogenated alicyclic hydrocarbon substance of the structural formula (I) or (II) contains one or more halogen atoms. In the present invention, the content of the halogenated alicyclic hydrocarbon substance refers to the sum of the mass percentages of the compounds satisfying the above structural formulas (I) and (II) contained in the polymeric MDI.

[0013] Specifically, the halogenated alicyclic hydrocarbon substances include one or more of alicyclic hydrocarbon substances substituted with a halogen element or multiple substitutions. Further, the halogenated alicyclic hydrocarbons are, for example, halogenated methylcyclohexane, halogenated methylcyclohexene, cyclohexane, cyclohexene, methylcyclohexane, methylcyclohexene, halogenated methylcyclohexane, and halogenated methylcyclohexene substituted with one or more halogen elements. Further, the halogen element is, for example, one or both of chlorine and bromine. Specifically, for example, the halogenated alicyclic hydrocarbon substances include one or more of monohalogenated or multiple halogenated chlorocyclohexane, bromocyclohexane, chlorocyclohexene, bromocyclohexene, etc.

[0014] Herein, the halomethyl group includes monohalomethyl group and polyhalomethyl group.

[0015] The present invention provides a polymeric MDI in which the content of a halogenated aliphatic cyclohydrocarbon substance is controlled within a specific lower range. The inventors have found that the halogenated aliphatic cyclohydrocarbon substance in the polymeric MDI will affect the application performance of the polymeric MDI in a polyurethane adhesive. If the content of the halogenated aliphatic cyclohydrocarbon substance in the polymeric MDI is too high, the operable time of the polyurethane adhesive will be too long. By using the polymeric MDI with a low content of a halogenated aliphatic cyclohydrocarbon substance in the polyurethane adhesive (such as a potting adhesive), the open time of the polyurethane adhesive can be improved. Specifically, it is beneficial to shorten the open time of the polyurethane adhesive. For example, in some embodiments, the open time can be shortened to between 25 and 36 minutes, thereby improving the construction efficiency of the adhesive.

[0016] At present, the MDI production process known in the art is mainly as follows: first, DAM (polyamine) and phosgene are used in a solvent for liquid-phase phosgenation reaction to obtain a reaction mixture; then the obtained reaction mixture is dephosgenated; then the dephosgenated reaction mixture is subjected to stripping heat treatment using HCl gas; the stripped reaction mixture is heated under negative pressure to remove the solvent; then the liquid after the solvent is further sent to a nitrogen stripping tower for nitrogen stripping treatment to obtain crude MDI; then the crude MDI is refined and separated to obtain the corresponding pure MDI and polymerized MDI products. Among them, in the prior art, the top condensate obtained after condensing the material extracted from the top of the nitrogen stripping tower is directly merged with the reaction mixture obtained by the liquid-phase phosgenation reaction to enter the phosgenation removal link. The inventors have found that the outlet temperatures of the phosgenation reaction, dephosgene, hydrogen chloride stripping and desolventizing processes are relatively low, only slightly higher than the boiling point of the solvent (e.g., chlorobenzene) at the equipment operating pressure or lower, resulting in the removal of components in these processes mainly consisting of solvents and other light components, such as phosgene, hydrogen chloride, carbon tetrachloride, etc. However, the operating pressure in the nitrogen stripping process is low and the temperature is high, and the top outlet material of the nitrogen stripping tower carries a large amount of MDI. The inventors have found through research that most of the halogenated aliphatic cyclic hydrocarbons (e.g., chlorocyclohexane, bromocyclohexane, chlorocyclohexene, bromocyclohexene, etc.) enter the top outlet material during the nitrogen stripping process and are removed, and subsequently enter the top condensate together through condensation, and only a small amount of halogenated aliphatic cyclic hydrocarbon substances enter the crude MDI. Since the MDI in the material extracted from the top of the nitrogen stripping tower is of high value, in the traditional process, this stream is directly condensed and recycled back to the system; the inventors found that this will cause the halogenated aliphatic cyclic hydrocarbon impurities to accumulate in the system during the continuous operation of the polymeric MDI preparation process system, and most of them will eventually enter the crude MDI and enter the polymeric MDI during the refining and separation process, thereby affecting the polymeric MDI product and its subsequent applications.

[0017] In addition, due to the relatively stable nature of halogenated aliphatic cyclic hydrocarbon impurities, they cannot be removed by reaction conversion methods in existing processes. At the same time, since the process for preparing polymerized MDI requires an unavoidable high-temperature process, this type of impurity cannot be solved at the source. Therefore, it is relatively difficult to remove halogenated aliphatic cyclic hydrocarbon impurities through the existing polymerized MDI process.

[0018] The present invention also provides a method for preparing the polymeric MDI with low halogenated alicyclic hydrocarbon content as described above, specifically, a method for reducing the content of halogenated alicyclic hydrocarbon in the polymeric MDI. The method comprises the following steps:

[0019] S1, performing phosgene removal treatment on a reaction mixture obtained by liquid-phase phosgenation reaction of polyamine and phosgene in a solvent;

[0020] S2, subjecting the reaction mixture after the treatment in step S1 to a stripping heat treatment using hydrogen chloride gas;

[0021] S3, performing solvent removal treatment on the reaction mixture after the treatment in step S2 to obtain a liquid after the solvent is removed;

[0022] S4, sending the liquid after the solvent is removed in step S3 into a nitrogen stripping tower for stripping with nitrogen, condensing the material extracted from the top of the nitrogen stripping tower to obtain a top condensate, and obtaining crude MDI in the bottom of the nitrogen stripping tower; refining and separating the crude MDI to obtain pure MDI and polymerized MDI;

[0023] S5, subjecting the tower top condensate in step S4 to a treatment for removing halogenated aliphatic cyclic hydrocarbon substances and then sending it to step S1 for mixing with the reaction mixture.

[0024] In the preparation method of the present invention, the condensate at the top of the nitrogen stripping tower is subjected to a treatment for removing halogenated aliphatic cyclopentane substances and then returned to step S1 to be mixed with the reaction mixture before phosgene removal for subsequent treatment, thereby avoiding the accumulation of halogenated aliphatic cyclopentane substances in the system and ultimately obtaining polymeric MDI with a low content of halogenated aliphatic cyclopentane substances.

[0025] In a preferred embodiment, in step S5, the removal of the halogenated aliphatic cyclic hydrocarbon substance comprises the following steps:

[0026] S5a, sending the tower top condensate to a flash heat exchanger for treatment, and the halogenated aliphatic cyclopentane substance separated from the tower top condensate enters the gas phase material of the flash heat exchanger; the liquid phase material obtained in the flash heat exchanger is a material rich in MDI, which is sent to the step S1 to be mixed with the reaction mixture before phosgene treatment, and circulated into the process system. Through the above step S5a, the accumulation of toxic and harmful impurities (such as halogenated aliphatic cyclopentane substances) in the system can be avoided, and the content of halogenated aliphatic cyclopentane substances in the final polymerized MDI product can be effectively reduced, which is conducive to improving the application performance and application safety of the polymerized MDI product.

[0027] Further preferably, the method further comprises step S5b: sending the gas phase material in step S5a into a distillation tower for treatment to separate the solvent in the gas phase material, obtaining a gas phase solvent portion at the top of the tower, and obtaining an impurity portion containing the halogenated aliphatic cyclohydrocarbon substance at the bottom of the tower, the impurity portion also containing part of the solvent and possibly other impurities. The impurity portion containing the halogenated aliphatic cyclohydrocarbon substance can be directly sealed for subsequent incineration treatment to avoid secondary hazards caused by other treatment methods.

[0028] More preferably, in step S5b, the gas phase solvent part is condensed to obtain a condensate, and part of the condensate is sent to a solvent storage tank, for example, it can be used as a recycled solvent in the liquid phase phosgenation reaction after subsequent impurity removal treatment; another part of the condensate of the gas phase solvent part is refluxed to the distillation tower of step S5b. Through the treatment in step S5b, part of the solvent can be separated and recovered, reducing solvent loss and reducing production costs.

[0029] In some embodiments, in step S5a, the flash heat exchanger is a rising film evaporator or a falling film evaporator;

[0030] Preferably, when the flash heat exchanger is a rising film evaporator, the operating pressure of the rising film evaporator is 20-60 kPa, such as 20, 25, 30, 35, 40, 45, 50, 55, 60 kPa, preferably 30-60 kPa, more preferably 40-50 kPa; the operating temperature is 80-150° C., such as 80° C., 90° C., 100° C., 110° C., 120° C., 130° C., 140° C., 150° C., etc., preferably 90-150° C., more preferably 110-130° C. The preferred process conditions are used to more thoroughly separate the halogenated aliphatic cyclopentane substances from the tower top condensate, and to further reduce the content of the halogenated aliphatic cyclopentane substances in the polymeric MDI product.

[0031] In a preferred embodiment, in step S5b, the distillation tower is a packed tower, and the number of theoretical plates of the packing is 20-50, preferably 25-50, such as 25, 30, 35, 40, 45, 50, etc., more preferably 30-40; the reflux ratio is controlled to be 0.2-0.6, such as 0.2, 0.3, 0.4, 0.5, 0.6, etc., preferably 0.4-0.5. The preferred process conditions are used to more thoroughly separate the halogenated aliphatic cyclopentane substances from the gas phase material obtained in step S5a, to further reduce the content of the halogenated aliphatic cyclopentane substances in the recovered solvent, and to reduce the content of the halogenated aliphatic cyclopentane substances in the polymerized MDI when the solvent is subsequently reused in the system. In some embodiments, in step S5b, the content of the halogenated aliphatic cyclopentane substances in the condensate obtained after the gas phase solvent portion is condensed can be controlled to be less than 5ppm. In step S5b, the filler in the distillation tower can be the filler commonly used in the art, such as metal structured packing (M500Y, M452Y, M252Y, etc.), metal random packing (IR, IMTP, Raschig ring, rectangular saddle ring, ball ring, etc.), etc., without any particular limitation.

[0032] In some embodiments, in step S5b, the bottom of the distillation tower is provided with a reboiler, and the top of the tower is provided with a condenser;

[0033] In some embodiments, the gas phase fraction at the outlet of the reboiler is controlled to be between 10-20%, such as 10%, 12%, 15%, 17%, 20%, etc., preferably 10-16%, such as 12-16%;

[0034] In some embodiments, the operating pressure at the top of the distillation tower is 25-50 kPa, for example, 20 kPa, 25 kPa, 30 kPa, 35 kPa, 40 kPa, 45 kPa, 50 kPa, etc., preferably 30-50 kPa, and more preferably 35-40 kPa; the preferred operating conditions are used to more thoroughly separate the halogenated aliphatic cyclic hydrocarbon substances.

[0035] In some embodiments, the operating temperature of the distillation tower kettle is 100-140°C, such as 100°C, 110°C, 120°C, 130°C, 140°C, etc., preferably 110-130°C; using the preferred operating conditions is conducive to more thoroughly separating the halogenated aliphatic cyclic hydrocarbon substances.

[0036] In some embodiments, the operating temperature of the condenser at the top of the distillation tower is 30°C-70°C, preferably 40-50°C.

[0037] In the present invention, polyamine refers to a mixture of diaminodiphenylmethane and polyphenylpolymethylenepolyamine (DAM), which can also be referred to as diphenylmethane series diamines and polyamines. The conventional process in the art can be used to prepare a reaction mixture by liquid-phase phosgenation reaction of polyamines and phosgene in a solvent, and the present invention has no particular restrictions on this; in many documents, the preparation of polymeric MDI by liquid-phase phosgenation reaction of polyamines and phosgene in a solvent is described in detail, such as CN116217439A, CN111961185B, CN108147979B, CN116034102A, CN104755458B, CN111170891B, etc. In some embodiments, the solvent used for liquid-phase phosgenation reaction is, for example, one or more of chlorobenzene, dichlorobenzene, diethyl carbonate, and cyclohexanone, preferably chlorobenzene. In some embodiments, for reference, the conditions for liquid phase phosgenation reaction include: reaction temperature of 60-160° C., reaction pressure of 2-30 bar, mass ratio of polyamine to solvent of 1:(1.1-5), and mass ratio of polyamine to phosgene of 1:(1.1-5).

[0038] In the preparation method of the present invention, the main improvement is that in step S5, the top condensate obtained by condensing the material produced from the top of the nitrogen stripping tower is treated to separate the halogenated aliphatic cyclohydrocarbon substances therein, and after the halogenated aliphatic cyclohydrocarbon substances are separated, the material is returned to step S1 to enter the process system. The corresponding process operations and process conditions in steps S1-S4 of the preparation method of the present invention can be carried out using the corresponding conventional process operations and conditions in the art, and there is no particular limitation on this.

[0039] In some embodiments, in step S1, the phosgene removal treatment is to heat treat the reaction mixture to remove phosgene; preferably, the temperature of the heat treatment is 100-150°C, for example, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, etc.

[0040] In some embodiments, in step S2, the temperature of the steam stripping heat treatment with hydrogen chloride gas is 100-200°C, for example, 100°C, 120°C, 140°C, 160°C, 180°C, 200°C, etc., the residence time is preferably 1-20min, for example, 1min, 5min, 10min, 15min, 20min, and the mass ratio of hydrogen chloride to the reaction mixture is 0.01-0.1, for example, 0.01, 0.05, 0.1, etc.

[0041] In some embodiments, in step S3, the solvent removal treatment is to remove the solvent by heating under negative pressure, preferably under the conditions of an operating pressure of 20-50 kPa (e.g., 20 kPa, 30 kPa, 40 kPa, 50 kPa, etc.) and a temperature of 120-240°C (e.g., 120°C, 150°C, 200°C, 240°C, etc.).

[0042] In some embodiments, in step S4, the operating pressure of the nitrogen stripping tower is 20-60 kPa, such as 20 kPa, 30 kPa, 40 kPa, 50 kPa, 60 kPa; the temperature is 150-230°C, such as 150°C, 180°C, 200°C, 230°C, etc.; the mass ratio of nitrogen to the liquid after the solvent is removed (stripping mass ratio) is 0.005-0.1, such as 0.005, 0.01, 0.05, 0.1, etc. The temperature at which the gas phase at the top of the nitrogen stripping tower is condensed is 20-60°C, such as 20°C, 30°C, 40°C, 50°C, 60°C, etc.

[0043] In the present invention, the pressure involved refers to absolute pressure unless otherwise specified.

[0044] In some embodiments, the refining and separation of crude MDI in step S4 is carried out in a distillation tower, and the process conditions of the distillation tower include, for example: the bottom temperature is controlled at 180-250°C, such as 180°C, 200°C, 230°C, 250°C, etc., and the top pressure is controlled at 10-1000Pa, such as 10Pa, 50Pa, 100Pa, 1000Pa, etc., to obtain a polymerized MDI product in the bottom of the tower.

[0045] In some implementation modes, in step S4, the content of the halogenated aliphatic cyclic hydrocarbon substance in the tower top condensate is between 10-10000 ppm.

[0046] By adopting the preparation method of the present invention, the content of halogenated aliphatic cyclohydrocarbon substances in polymeric MDI can be reduced, and polymeric MDI with a halogenated aliphatic cyclohydrocarbon substance content that meets the required requirements can be obtained.

[0047] As mentioned above, some impurities will inevitably be generated during the production process of DAM. After phosgenation, hydrogen chloride stripping and high temperature treatment in the desolventizing stage, halogenated aliphatic cyclic hydrocarbon impurities will be generated. The inventors found that because the boiling point of some substances is higher than or close to the boiling point of the solvent (such as chlorobenzene), it is impossible to completely remove them during the desolventizing process, and a small amount of halogenated aliphatic cyclic hydrocarbons will enter the polymerized MDI product. On the one hand, since such substances are generally volatile, when used downstream, if the temperature is too high, they will evaporate into the environment, bringing potential safety risks; on the other hand, the inventors have found that such substances will affect the application performance of the product, especially the open time (operable time) after the reaction of polymerized MDI and white material (polyether polyol, etc.) when used in the downstream potting glue field. If the content of such impurities is too high, the open time will be too high, affecting the process operation and reducing the construction efficiency. Therefore, reducing the content of halogenated aliphatic cyclic hydrocarbon substances in the polymerized MDI product is conducive to improving the application performance and safety of the polymerized MDI product in the downstream and reducing the impact on the environment.

[0048] The present invention also provides a method for improving the open time of a polyurethane adhesive, wherein the raw material used in the polyurethane adhesive includes polymerized MDI, and the content of halogenated alicyclic hydrocarbon substances in the polymerized MDI is controlled to be ≤15ppm, preferably ≤10ppm, more preferably ≤5ppm, and further preferably ≤1ppm. The inventors have found that by controlling the content of halogenated alicyclic hydrocarbon substances in the polymerized MDI used in the polyurethane adhesive to meet the above requirements, it is beneficial to improve the open time of the polyurethane adhesive. Specifically, for example, the open time can be shortened to not be too long, and compared with the polymerized MDI whose content of halogenated alicyclic hydrocarbon substances does not meet the above requirements, the open time can be shortened, and the construction efficiency can be improved, for example, the open time can be shortened to between 25-36 minutes.

[0049] Furthermore, the halogenated aliphatic cyclic hydrocarbon substance is one or more compounds having the following structural formulas (I) and (II):

[0050]

[0051] wherein each R in the structural formula (I) and (II) is independently hydrogen, methyl, halomethyl or halogen, and at least one of the R in the structural formula (I) or (II) is halogen or halomethyl;

[0052] Specifically, for example, the halogenated alicyclic hydrocarbon is one or more of halogenated methylcyclohexane, halogenated methylcyclohexene, cyclohexane, cyclohexene, methylcyclohexane, methylcyclohexene, halogenated methylcyclohexane, and halogenated methylcyclohexene substituted with one or more halogen elements;

[0053] For example, the halogen element is one or both of chlorine and bromine.

[0054] Specifically, for example, in some embodiments, the halogenated aliphatic cyclic hydrocarbon substance includes one or more of monohalogenated or polyhalogenated chlorocyclohexane, bromocyclohexane, chlorocyclohexene, bromocyclohexene, and the like.

[0055] In some embodiments, in the method for improving the open time of the polyurethane adhesive, the content of the halogenated aliphatic cyclic hydrocarbon substance in the polymerized MDI used is controlled to be 0-15ppm, for example, 0ppm, 0.05ppm, 0.1ppm, 1ppm, 2ppm, 3ppm, 4ppm, 5ppm, 6ppm, 7ppm, 8ppm, 9ppm, 10ppm, 11ppm, 12ppm, 13ppm, 14ppm or 15ppm, etc.; preferably 0-10ppm; more preferably 0-5ppm; further preferably 0-1ppm, for example 0ppm, 0.0001ppm, 0.001ppm, 0.01ppm, 0.05ppm, 0.1ppm, 0.3ppm, 0.5ppm, 0.7ppm, 1ppm, etc.

[0056] In some embodiments, in the method for improving the open time of the polyurethane adhesive, the content of the halogenated alicyclic hydrocarbon substance in the polymerized MDI used is controlled to be >0 and ≤15ppm, for example, 0.0001-15ppm, 0.01-15ppm, 0.1-15ppm, 0.5-15ppm, etc. In some embodiments, the content of the halogenated alicyclic hydrocarbon substance in the polymerized MDI used is controlled to be >0 and ≤10ppm, for example, 0.0001-10ppm, 0.01-10ppm, 0.1-10ppm, 0.5-10ppm, etc. In some embodiments, the content of the halogenated alicyclic hydrocarbon substance in the polymerized MDI used is controlled to be >0 and ≤5ppm, for example, 0.0001-5ppm, 0.01-5ppm, 0.1-5ppm, 0.5-5ppm, etc. In some embodiments, the content of halogenated aliphatic cyclic hydrocarbon substances in the polymeric MDI used is controlled to be >0 and ≤1 ppm, for example, 0.0001-1 ppm, 0.01-1 ppm, 0.1-1 ppm, 0.5-1 ppm, etc.

[0057] In the method for improving the open time of the polyurethane adhesive provided by the present invention, the polymeric MDI used can be prepared by the method for preparing polymeric MDI with low halogenated aliphatic cyclic hydrocarbon content described above.

[0058] Specifically, the raw materials of the polyurethane adhesive include component A (black material) and component B (white material), wherein the component A at least includes the polymerized MDI as the black material; and the component B at least includes polyether polyol as the white material. The formula composition of the polyurethane adhesive based on polymerized MDI (including but not limited to the selection and dosage of each component) can adopt the conventional composition in the art, and there is no special restriction on this. The key of the present invention is to control the content of halogenated aliphatic cyclic hydrocarbon substances in the polymerized MDI used in this type of polyurethane adhesive to meet the specific requirements of the present invention, so as to achieve the purpose of improving the open time.

[0059] In some embodiments, as an example, the mass ratio of the component A to the component B is 1:(1-10), for example, 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, etc.

[0060] In some embodiments, as an example, in addition to the polyether polyol, component B may also contain other components that are allowed to be added in the field of polyurethane adhesives, such as but not limited to flame retardants, plasticizers, antioxidants, modifiers, defoaming agents, grafting agents, etc. The amounts of these components can be specifically determined according to application requirements. In some examples, the mass proportion of these components in component B is less than 0.5%.

[0061] The polyether polyol used in the polyurethane adhesive may be any polyether polyol conventionally used in the art, and there is no particular limitation on this. For example, the polyether polyol in component B may be one or more of polyoxyethylene polyol, polyoxypropylene polyol, polytetrahydrofuran and copolyether polyol thereof, and the molecular molar mass of the polyether polyol may be, for example, 200-10000 g / mol.

[0062] Those skilled in the art know that the above-mentioned polyurethane adhesive can be used in, for example, the fields of electronic appliances, aviation equipment, medical industry, construction, etc.

[0063] In this article, the "open time" refers to the time interval from the application of the polyurethane adhesive to the surface of the adherend to the time when the adhesive can no longer be effectively applied, where the effective application operation includes brushing or rolling the adhesive or transferring it to another adherend surface, etc. The effective time for the operation is called the open time; in other words, the open time can also be understood as the maximum time that the polyurethane adhesive can be left in the air after being applied to the surface of the adherend before the adherend is bonded.

[0064] In another aspect, the present invention further provides a polyurethane adhesive, comprising component A and component B, wherein component A at least comprises the polymerized MDI described above, and component B at least comprises a polyether polyol, and preferably, the mass ratio of component A to component B is 1:1-10. Other descriptions of the polyurethane adhesive can refer to the corresponding descriptions in the description of the method for improving the open time of the polyurethane adhesive in the above text, and will not be repeated here.

[0065] The technical solution provided by the present invention has the following beneficial effects:

[0066] 1) The present invention provides a polymeric MDI with a low halogenated aliphatic cyclohydrocarbon content in which the content of the halogenated aliphatic cyclohydrocarbon content is controlled. When the polymeric MDI provided by the present invention is used in a polyurethane adhesive, the open time can be significantly improved compared to the use of polymeric MDI without controlling the content of the low halogenated aliphatic cyclohydrocarbon content, and the excessively long open time can be shortened, thereby improving the construction efficiency.

[0067] 2) The method for preparing polymeric MDI with low halogenated aliphatic cyclopentane content provided by the present invention is to separate the MDI, solvent and halogenated aliphatic cyclopentane impurities from the top condensate of the nitrogen stripping tower during the production process of polymeric MDI by treating it separately, and the separated MDI-rich logistics are circulated back to the system, the solvent can enter the solvent storage tank for subsequent reuse, and the concentrated part containing halogenated aliphatic cyclopentane impurities no longer enters the process system. The scheme proposed by the present invention has a simple process flow and operation, less modification to the existing process, low difficulty in transformation, and will not have any adverse effects on the existing process. At the same time, the scheme of the present invention can avoid the accumulation of halogenated aliphatic cyclopentane impurities in the system, effectively reduce the content of halogenated aliphatic cyclopentane impurities in the polymeric MDI produced, and can control the content of halogenated aliphatic cyclopentane impurities in the polymeric MDI within the required range, which can improve the application performance of the polymeric MDI product and the downstream application safety.

[0068] 3) The method for preparing polymeric MDI with low halogenated aliphatic cyclic hydrocarbon content provided by the present invention has the characteristics of simple process, low operating cost, and easy operation. BRIEF DESCRIPTION OF THE DRAWINGS

[0069] Figure 1 Schematic diagram of a process for removing halogenated aliphatic cyclic hydrocarbon impurities in one embodiment.

[0070] Among them, E1 is a flash heat exchanger, E2 is a tower top condenser, E3 is a tower bottom reboiler, C1 is a distillation tower, P1 is a reboiler circulation and extraction pump, and D1 is a halogenated aliphatic cyclic hydrocarbon impurity storage tank. DETAILED DESCRIPTION

[0071] In order to facilitate the understanding of the present invention, the present invention will be further described below in conjunction with examples. It should be understood that the following examples are only for a better understanding of the present invention and do not mean that the present invention is limited to the following examples.

[0072] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the invention belongs. The term "and / or" used herein includes any and all combinations of one or more of the associated listed items.

[0073] Where specific experimental steps or conditions are not specified in the examples, the corresponding conventional experimental steps or conditions in the art can be used. The reagents or instruments used without specifying the manufacturer are all conventional products that can be purchased commercially.

[0074] The test method of halogenated aliphatic cyclic hydrocarbon content is as follows: dilute the sample to be tested by 10 times of its mass with dichloromethane and then directly use gas chromatography for analysis and determination. The test conditions are as follows:

[0075] Gas chromatograph detector: Agilent 7890A, chromatographic column HP-5 (30m×0.25um×320μm). Chromatographic conditions: column temperature: 50℃ for 0.5min, 5℃ / min to 80℃ for 1min; 10℃ / min to 280℃ for 10min; injection port temperature: 280℃, detector temperature: 295℃; septum purge gas flow rate: 3.0mL / min; carrier gas (nitrogen) flow rate: 3mL / min; air flow rate: 350mL / min; hydrogen flow rate: 35mL / min; tail gas (nitrogen) flow rate: 25mL / min; split injection, split ratio 1:10, injection volume 0.5μL.

[0076] In the following embodiments, the content of halogenated aliphatic cyclic hydrocarbon substances refers to the sum of the mass contents of chlorocyclohexane, bromocyclohexane, chlorocyclohexene and bromocyclohexene, wherein the halogenated aliphatic cyclic hydrocarbon substances include the corresponding monohalogenated and polyhalogenated compounds.

[0077] Test method for the open time of potting glue: measured by the Ecoray GT-2 gel time tester. Mix component A and component B and immediately add them into the test tube as the test sample and immediately perform the following operations: immerse the test tube in a constant temperature dish; insert a stirring glass rod into the test tube, and connect the glass rod to a torsion metal wire, where the metal wire is driven by a synchronous motor, and the motor rotates at a rate of 1 rpm. The timing starts, and the gel tester monitors the test process until the gel point is reached. The gel time displayed is the open time.

[0078] Ingredients:

[0079] Diphenylmethane series diamines and polyamines (DAM): Wanhua Chemical (Ningbo) Co., Ltd., purity>99.99%; specifically, the preparation method of DAM is as follows: aniline and 32wt% hydrochloric acid are mixed at a molar ratio of 1:0.3 at 60°C and 1 bar to generate aniline hydrochloride, which is then reacted with formaldehyde (the molar ratio of formaldehyde to aniline is 0.4:1) at 120°C for 2h, and a transposition liquid is obtained through a condensation transposition process, which is neutralized with a 32wt% sodium hydroxide aqueous solution, and then washed with water to obtain polyamines, which are then distilled and stripped at 200°C and 10kpa to obtain DAM.

[0080] Chlorobenzene: Wanhua Chemical (Ningbo) Co., Ltd., purity >99.9%.

[0081] Phosgene: Wanhua Chemical (Ningbo) Co., Ltd., purity>95.0%.

[0082] Polyether polyol: Hydrophobic polyether polyol D3201, manufacturer: Dow.

[0083] Example 1

[0084] A diphenylmethane series diamine and polyamine (DAM) are mixed with chlorobenzene to obtain a mixed solution with an amine concentration of 30 wt%, and a phosgene chlorobenzene solution with a phosgene concentration of 60 wt% (the mass ratio of DAM to phosgene is 1:2.4) is added to the mixed solution to react at 3 barg and 100° C. for 1 hour to obtain a reaction mixture; then the reaction mixture obtained by the reaction is dephosgeneated at 0.1 MPa and 135° C., and then stripped with hydrogen chloride at a temperature of 180° C., the mass ratio of HCl to the reaction mixture is 0.05, and the residence time is 5 min; then the reaction mixture after the stripping treatment is dechlorobenzened at 35 kpa and 205° C., and the MDI after the dechlorobenzene treatment (i.e., the reaction solution after the solvent removal) is sent to a nitrogen stripping tower for treatment at 40 kpa and 200° C., and the mass ratio of nitrogen to the reaction solution after the solvent removal is controlled to be 0.03;

[0085] The material extracted from the top of the nitrogen stripping tower is condensed to obtain a top condensate, the content of halogenated aliphatic cyclic hydrocarbon substances in the top condensate is 1000ppm, the top condensate is sent to a rising film evaporator E1, and treated at an operating pressure of 40kpa and a temperature of 120°C, the liquid phase material is sent to a phosgene removal step to be mixed with the reaction mixture before phosgene removal, and the gas phase material obtained by the rising film evaporator E1 is sent to a distillation tower C1; the distillation tower C1 is a packed tower, the packing is Sulzer M452Y metal structured packing, the number of theoretical plates is 40, the reflux ratio is 0.5, the bottom of the distillation tower C1 is provided with a reboiler E3, and the top of the tower is provided with a condenser E2, the top operating pressure of the distillation tower C1 is 35kpa, the bottom temperature is 120°C, the gas phase fraction at the outlet of the reboiler E3 is 10%, and the operating temperature of the condenser E2 is 45°C. The gaseous chlorobenzene is extracted from the top of the distillation tower C1. After the gaseous chlorobenzene is condensed at 45°C, part of the chlorobenzene condensate is sent to the crude chlorobenzene storage tank, and part of it is refluxed to the distillation tower C1. The content of halogenated aliphatic cyclopentane substances in the chlorobenzene condensate is 0.5ppm. The impurity part containing the halogenated aliphatic cyclopentane substances extracted from the bottom of the distillation tower C1 enters the halogenated aliphatic cyclopentane impurity storage tank D1.

[0086] The crude MDI (chlorobenzene content is 800 ppm) obtained in the bottom of the nitrogen stripping tower is sent to the downstream distillation tower for refining. The process conditions of the distillation tower are a top pressure of 20 Pa and a bottom temperature of 200°C. The polymerized MDI product is obtained in the bottom of the distillation tower.

[0087] The content of halogenated aliphatic cyclic hydrocarbon substances in the polymeric MDI product prepared by the process of Example 1 is 1 ppm.

[0088] The polymeric MDI prepared in Example 1 was used to prepare a potting compound, wherein component A (black material) was the polymeric MDI prepared in Example 1, and component B (white material) was a polyether polyol. Component A and component B were mixed in a mass ratio of 1:5, and the open time of the potting compound was measured to be 30 minutes.

[0089] Example 2

[0090] The process was carried out with reference to Example 1, except that: some process conditions were changed on the basis of Example 1, specifically, the operating pressure of the rising film evaporator was adjusted to 20 kPa, and the temperature was adjusted to 80°C; the number of theoretical plates of the distillation tower used to process the gas phase material of the rising film evaporator was 20, the reflux ratio was 0.2, the top operating pressure of the distillation tower was 25 kPa, and the bottom temperature was 130°C. The rest of the operations were the same as in Example 1.

[0091] Results: In Example 2, the content of halogenated aliphatic cyclic hydrocarbon substances in the chlorobenzene condensate was 50 ppm, and the content of halogenated aliphatic cyclic hydrocarbon substances in the finally obtained polymeric MDI product was 12 ppm.

[0092] The polymeric MDI prepared in Example 2 was prepared into a potting compound by referring to the operation in Example 1, and the open time of the obtained potting compound was measured to be 36 minutes.

[0093] Example 3

[0094] The process was carried out with reference to Example 1, except that: some process conditions were changed on the basis of Example 1, specifically, the operating pressure of the rising film evaporator was adjusted to 35 kPa, and the temperature was adjusted to 105°C; the number of theoretical plates of the distillation tower used to process the gas phase material of the rising film evaporator was 30, the reflux ratio was 0.3, the top operating pressure of the distillation tower was 25 kPa, and the bottom temperature was 130°C. The rest of the operations were the same as in Example 1.

[0095] Results: In Example 3, the content of halogenated aliphatic cyclic hydrocarbon substances in the chlorobenzene condensate was 30 ppm, and the content of halogenated aliphatic cyclic hydrocarbon substances in the finally obtained polymeric MDI product was 8 ppm.

[0096] The polymeric MDI prepared in Example 3 was prepared into a potting compound by referring to the operation in Example 1, and the open time of the obtained potting compound was measured to be 34 minutes.

[0097] Example 4

[0098] The process was carried out with reference to Example 1, except that: some process conditions were changed on the basis of Example 1, specifically, the operating pressure of the rising film evaporator was adjusted to 35 kPa, and the temperature was adjusted to 110°C; the number of theoretical plates of the distillation tower used to process the gas phase material of the rising film evaporator was 35, and the reflux ratio was 0.4. The rest of the operations were the same as in Example 1.

[0099] Results: In Example 4, the content of halogenated aliphatic cyclic hydrocarbon substances in the chlorobenzene condensate was 5 ppm, and the content of halogenated aliphatic cyclic hydrocarbon substances in the finally obtained polymeric MDI product was 2 ppm.

[0100] The polymeric MDI prepared in Example 4 was prepared into a potting compound by referring to the operation in Example 1, and the open time of the obtained potting compound was measured to be 32 minutes.

[0101] Comparative Example 1

[0102] The diphenylmethane series diamine and polyamine (DAM) were mixed with chlorobenzene to obtain a mixed solution with an amine concentration of 30 wt%, and a phosgene chlorobenzene solution with a phosgene concentration of 60 wt% (the mass ratio of DAM to phosgene was 1:2.4) was added to the mixed solution, and the mixture was reacted at 3 barg and 100° C. for 1 h to obtain a reaction mixture; then the reaction mixture was dephosgeneated at 0.1 MPa and 135° C., and then stripped with hydrogen chloride at a temperature of 180° C., the mass ratio of HCl to the reaction mixture was 0.05, and the residence time was 5 min; then the stripped reaction mixture was subjected to a saturation treatment at 35 kpa and 205° C. The dechlorobenzene treatment is carried out, and the MDI after dechlorobenzene (i.e., the reaction liquid after desolventization) is sent to a nitrogen stripping tower for treatment at 40 kPa and 200°C, and the mass ratio of nitrogen to the reaction liquid after desolventization is controlled to be 0.03; the material extracted from the top of the nitrogen stripping tower is condensed to obtain a top condensate, and the top condensate is directly sent to the phosgene removal step to be mixed with the reaction mixed liquid before dephosgeneration; the crude MDI (chlorobenzene content is 800 ppm) obtained in the bottom of the nitrogen stripping tower is sent to a distillation tower for refining. The process conditions of the distillation tower are a top pressure of 20 Pa and a bottom temperature of 200°C, and a polymerized MDI product is obtained in the bottom of the distillation tower.

[0103] Results: The content of halogenated aliphatic cyclic hydrocarbons in the polymerized MDI product was 20 ppm. The polymerized MDI obtained in Comparative Example 1 was used to prepare a potting compound according to the operation of Example 1, and the open time of the potting compound was measured to be 40 minutes.

[0104] From the above experimental results, it can be seen that in the embodiments of the present invention, the content of halogenated aliphatic cyclohydrocarbon substances in the polymerized MDI is controlled to be less than 15ppm. Compared with Comparative Example 1, the application in the potting glue can shorten the open time from 40min in Comparative Example 1 to between 25-36min, which can take into account good construction operability and construction efficiency. Preferably, in Examples 1-4, the content of halogenated aliphatic cyclohydrocarbon substances in the polymerized MDI is 1, 12, 8, and 2ppm, respectively, and the open time of the obtained potting glue is 30, 36, 34, and 32min, respectively, and the open time is about 30 minutes; it can be seen that the lower the content of halogenated aliphatic cyclohydrocarbon substances, the more obvious the shortening of its open time, and it is still between 25-36min.

[0105] It is easy to understand that the above embodiments are only examples for clear explanation and do not mean that the present invention is limited thereto. For ordinary technicians in the relevant field, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived from this are still within the protection scope of the present invention.

Claims

1. A polymeric MDI having a low content of halogenated aliphatic cyclic hydrocarbon substances, characterized in that: The content of halogenated aliphatic cyclic hydrocarbon substances in the polymeric MDI is ≤15ppm, preferably ≤10ppm, more preferably ≤5ppm, and further preferably ≤1ppm; The content of halogenated aliphatic cyclic hydrocarbon substances in the polymeric MDI is, for example, 0-15 ppm, for example, >0 and ≤15 ppm, for example, >0 and ≤10 ppm, for example, >0 and ≤5 ppm, for example, >0 and ≤1 ppm.

2. The polymeric MDI according to claim 1, characterized in that The halogenated aliphatic cyclic hydrocarbon substance is one or more compounds having the following structural formula (I) and (II): wherein each R in the structural formula (I) and (II) is independently hydrogen, methyl, halomethyl or halogen, and at least one of the R in the structural formula (I) or (II) is halogen or halomethyl; For example, the halogen element is one or both of chlorine and bromine.

3. The method for preparing polymeric MDI with low halogenated aliphatic cyclic hydrocarbon content according to claim 1 or 2, characterized in that: The steps include: S1, performing phosgene removal treatment on a reaction mixture obtained by liquid-phase phosgenation reaction of polyamine and phosgene in a solvent; S2, subjecting the reaction mixture after the treatment in step S1 to a stripping heat treatment using hydrogen chloride gas; S3, performing solvent removal treatment on the reaction mixture after the treatment in step S2 to obtain a liquid after the solvent is removed; S4, sending the liquid after the solvent is removed in step S3 into a nitrogen stripping tower for stripping with nitrogen, condensing the material extracted from the top of the nitrogen stripping tower to obtain a top condensate, and obtaining crude MDI in the bottom of the nitrogen stripping tower; refining and separating the crude MDI to obtain pure MDI and polymerized MDI; S5, subjecting the tower top condensate in step S4 to a treatment for removing halogenated aliphatic cyclic hydrocarbon substances and then sending it to step S1 for mixing with the reaction mixture.

4. The preparation method according to claim 3, characterized in that: In step S5, the removal of the halogenated aliphatic cyclic hydrocarbon substances comprises the following steps: S5a, sending the tower top condensate to a flash heat exchanger for treatment, and the halogenated aliphatic cyclic hydrocarbon substances separated from the tower top condensate enter the gas phase material; sending the liquid phase material obtained in the flash heat exchanger to the step S1 to be mixed with the reaction mixture; Preferably, the method further comprises step S5b: sending the gas phase material in step S5a into a distillation tower for treatment to separate the solvent in the gas phase material, obtaining a gas phase solvent portion at the top of the tower, and obtaining an impurity portion containing the halogenated aliphatic cyclic hydrocarbon substance at the bottom of the tower; further preferably, in step S5b, condensing the gas phase solvent portion to obtain a condensate, and sending part of the condensate into a solvent storage tank; Preferably, in step S5a, the flash heat exchanger is a rising film evaporator or a falling film evaporator; when the flash heat exchanger is a rising film evaporator, the operating pressure of the rising film evaporator is 20-60 kPa, preferably 30-60 kPa, more preferably 40-50 kPa; the operating temperature is 80-150°C, preferably 90-150°C, more preferably 110-130°C.

5. The preparation method according to claim 4, characterized in that: In step S5b, the distillation tower is a packed tower, and the number of theoretical plates of the packing is 20-50, preferably 25-50, and more preferably 30-40; the reflux ratio is controlled to be 0.2-0.6, preferably 0.4-0.

5.

6. The preparation method according to claim 5, characterized in that: In step S5b, the bottom of the distillation tower is provided with a reboiler, and the top of the tower is provided with a condenser; Preferably, the gas phase fraction at the outlet of the reboiler is controlled between 10-20%, preferably 10-16%; Preferably, the operating pressure at the top of the distillation tower is 25-50 kPa, preferably 30-50 kPa, more preferably 35-40 kPa; Preferably, the operating temperature of the distillation tower reactor is 100-140°C, preferably 110-130°C; Preferably, the operating temperature of the condenser at the top of the distillation tower is 30°C-70°C, preferably 40-50°C.

7. The preparation method according to any one of claims 3 to 6, characterized in that: Preferably, in step S1, the phosgene removal treatment is to heat-treat the reaction mixture to remove phosgene, and the temperature of the heat treatment is 100-150° C.; Preferably, in step S2, the temperature of the stripping heat treatment with hydrogen chloride gas is 100-200° C., the residence time is preferably 1-20 min, and the mass ratio of hydrogen chloride to the reaction mixture is 0.01-0.1; Preferably, in step S3, the solvent removal treatment is carried out under the conditions of an operating pressure of 20-50 kPa and a temperature of 120-240° C.; Preferably, in step S4, the operating pressure of the nitrogen stripping tower is 20-60 kPa, the temperature is 150-230° C., and the mass ratio of nitrogen to the liquid after the solvent is removed is 0.005-0.1; Preferably, the solvent used for the liquid phase phosgenation reaction is one or more of chlorobenzene, dichlorobenzene, diethyl carbonate and cyclohexanone.

8. The preparation method according to any one of claims 4 to 7, characterized in that: In step S4, the content of the halogenated aliphatic cyclic hydrocarbon substance in the tower top condensate is between 10-10000 ppm; And / or, in step S5b, the content of the halogenated aliphatic cyclic hydrocarbon substance in the condensate obtained after the gas phase solvent is partially condensed is less than 5 ppm.

9. A method for improving the open time of a polyurethane adhesive, wherein the raw material used in the polyurethane adhesive includes polymerized MDI, characterized in that: Controlling the content of halogenated aliphatic cyclic hydrocarbon substances in the polymeric MDI to ≤15ppm, preferably ≤10ppm, more preferably ≤5ppm, and further preferably ≤1ppm; The content of halogenated aliphatic cyclic hydrocarbon substances in the polymeric MDI is, for example, 0-15 ppm, for example, >0 and ≤15 ppm, for example, >0 and ≤10 ppm, for example, >0 and ≤5 ppm, for example, >0 and ≤1 ppm; The halogenated aliphatic cyclic hydrocarbon substance is one or more compounds having the following structural formula (I) and (II): Wherein, each R in the structural formula (I) and (II) is independently hydrogen, methyl, halomethyl or halogen, and at least one of the R in the structural formula (I) or (II) is halogen or halomethyl; for example, the halogen element is one or both of chlorine and bromine; Preferably, the raw materials of the polyurethane adhesive include component A and component B, wherein the component A includes at least the polymerized MDI; the component B includes at least a polyether polyol; preferably, the mass ratio of the component A to the component B is 1:1-10.

10. A polyurethane adhesive, characterized in that: The polyurethane adhesive comprises component A and component B, wherein component A comprises at least the polymerized MDI according to claim 1 or 2, and component B comprises at least polyether polyol. Preferably, the mass ratio of component A to component B is 1:1-10.

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