KR102154865B1 - Kit for Manufacturing Polyurethane Foam And Polyurethane Foam using the Same - Google Patents

Abstract

The present invention relates to a kit for manufacturing polyurethane foam and a method for manufacturing polyurethane foam using the same. More particularly, the present invention relates to a kit for manufacturing polyurethane foam, which separately accommodates: component A including MDI and graphite; and component B including a polyol, calcium silicate and a dispersant, and to a method for manufacturing polyurethane foam using the same.

Description

Kit for manufacturing polyurethane foam and method for manufacturing polyurethane foam using the same {Kit for Manufacturing Polyurethane Foam And Polyurethane Foam using the Same}

The present invention relates to a kit for producing a polyurethane foam and a method for producing a polyurethane foam using the same, and more particularly, to a component A including MDI and graphite; And the component B comprising a polyol, calcium silicate and a dispersant; characterized in that the separation and receiving, a polyurethane foam production kit and a polyurethane foam production method using the same.

The field-installed polyurethane foam, which is filled in empty spaces such as door gaps, has excellent insulation performance and is used in many places such as frozen warehouses, distribution warehouses, and general buildings, but it has a disadvantage that is vulnerable to fire and is therefore limitedly used.

Existing polyurethane foam is a mixture of 2 to 3 types of polyether polyol, foaming agent (HCFC 141b, etc.), catalyst, flame retardant, foam stabilizer, etc., and a resin premix and polyisocyanate prepared in advance in a volume ratio of 1:1. It was common to spray and use it on the skin surface (ceiling, wall, etc.) of the site using a high-pressure blower.

At this time, tris (chloroisopropyl) phosphate and Daihichi's CR-530 are mainly used as flame retardants, but it is known that there is no significant improvement in flame retardancy.

As the blowing agent, as a physical blowing agent, 1.1-dichloro-1-1-fluoro-ethane (trade name 141b) of low boiling point hydrochlorofluorocarbon (HCFC) was used, but recently, 141b type blowing agent is bad for global warming. As it turned out to have an effect, its use was limited.

Japanese Patent Publication No. Hei 5-176817 Japanese Patent Publication No. Hei 5-253402

In order to solve the above problems, it is an object of the present invention to provide a kit for manufacturing a polyurethane foam foam having high flame retardancy, eco-friendly, and excellent insulation performance, and a method for manufacturing a polyurethane foam using the same.

In order to achieve the above object, the present invention A component comprising MDI and graphite; And a polyol, calcium silicate, and component B including a dispersant; it provides a kit for producing a polyurethane foam, which is characterized in that it is separately accommodated.

At this time, the content of each component is preferably 40 to 50% by weight of polyol, 35 to 45% by weight of MDI, 5 to 10% by weight of graphite, 5 to 10% by weight of calcium silicate, and 1 to 5% by weight of a dispersant.

In addition, in order to achieve the above object, the present invention provides a method for producing a polyurethane foam, characterized in that the A component and the B component are injected into an empty space through a high-pressure foamer, and then foamed.

The kit for manufacturing polyurethane foam according to the present invention is to solve the problems caused by low heat resistance, flame retardancy, and emission of harmful gases of general polyurethane foam. It is an object of the present invention to provide a kit for producing polyurethane foam and a method for producing polyurethane foam using the same.

Hereinafter, the present invention will be described in detail with reference to embodiments of the present invention and drawings. These examples are only illustratively presented to explain the present invention in more detail, and it will be apparent to those of ordinary skill in the art that the scope of the present invention is not limited by these examples. .

In addition, unless otherwise defined, all technical and scientific terms used in the present specification have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs, and in case of conflict, the present specification including definitions The description of will take precedence.

In order to clearly describe the invention proposed in the drawings, parts not related to the description are omitted, and similar reference numerals are attached to similar parts throughout the specification. And, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary. In addition, "unit" described in the specification means one unit or block that performs a specific function.

In each step, the identification code (first, second, etc.) is used for convenience of description, and the identification code does not describe the order of each step, and each step does not clearly describe a specific sequence in the context. It may be implemented differently from the order specified above. That is, each of the steps may be performed in the same order as the specified order, may be performed substantially simultaneously, or may be performed in the reverse order.

Polyurethane foam production kit of the present invention, A component containing MDI and graphite; And a component B including polyol, calcium silicate and dispersant; At this time, the content of each component is preferably 40 to 50% by weight of polyol, 35 to 45% by weight of MDI, 5 to 10% by weight of graphite, 5 to 10% by weight of calcium silicate, and 1 to 5% by weight of a dispersant.

In addition, the polyurethane foam of the present invention can be prepared by injecting and interlocking the A component and B component into an empty space through a high-pressure foamer to foam. More specifically, preparing the component A by mixing MDI and graphite at RPM 500 to 1500 for 10 to 30 minutes, and then injecting it into a first container; Preparing the B component by mixing polyol, calcium silicate, and dispersant at RPM 500 to 1500 for 10 to 30 minutes, and then injecting it into a second container; And injecting and occluding the materials in the first container and the second container into an empty space through a high-pressure foamer to foam. Each component is examined in detail below.

The MDI (4,4-diphenylmethane diisocyanate) is a representative isocyanate compound, which reacts with a polyol to foam, hexamethylene diisocyanate, m-phenylene diisocyanate, 2,4-toluene diisocyanate (TDI) , Dianisidine diisocyanate, tolidin isocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane, chlorophenylene-2,4-diisocyanate, 1,5-naphthalene diisocyanate, ethylene diisocyanate, die Tyridene diisocyanate, propylene-1,2-diisocyanate, cyclohexylene-1,2-diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dimethoxy -4,4'-biphenylene diisocyanate, 3,3'-diphenyl-4,4'-biphenylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dichloro-4 ,4′-biphenylene diisocyanate, furfurylidene diisocyanate, and the like, and the catalyst may be at least one selected from the group consisting of triethylenediamine (TEDA), 1,4-diazabicyclo[2.2.2 ]Octane (DABCO), dimethylcyclohexylamine (DMCHA), or dimethylethanolamine (DMEA) may be substituted.

The content of the MDI is preferably 35 to 45% by weight of the total foam composition, and if it is more or less than this, foaming may not be properly performed or the hardness may be too low.

The graphite serves to increase the rigidity of the foam and prevent cracking while adding flame retardancy to the foamed foam, and the content is preferably 5 to 10% by weight of the total foam composition. If it is less than this, the functional effect of graphite may be deteriorated, and if it exceeds this, the foamability and heat insulation properties of the foamed foam may be deteriorated.

At this time, in order to increase miscibility with other components and increase incombustibility, the graphite may be a composite with zinc. The composite is obtained by dispersing an organometallic coupling agent and graphite in an aqueous medium, adding zinc chloride or zinc iodide to the dispersion, and drying to obtain a zinc/coupling agent/graphite composite, and then firing the dried composite. I can.

It is preferable to use the graphite modified by surface oxidation.For example, 1) a dry oxidation method in which an oxidizing agent gas such as water vapor, carbon dioxide, oxygen and ozone is brought into contact with graphite at a high temperature, and 2) graphite and an oxidizing agent (e.g. Hydrogen peroxide, nitric acid, sulfuric acid, etc.) There is wet oxidation in which a reagent solution reacts. In addition, there are electrochemical oxidation, ozone treatment, annealing, and microwave cooling plasma heat treatment.

의 화학식을 가지는 커플링제가 사용될 수 있으며, 상기 식에서, RO는 가수분해기 또는 기질 반응성기로, 상기 R은 탄소수 2 내지 10개이고, 상기 Z는 알루미늄, 실리콘, 티타늄, 아연 및 지르코늄으로 구성된 군에서 선택되는 1종 이상의 원소이며, 상기 R'는 지방족, 나프텐계 또는 방향족의 열가소성 작용기로서, 탄소수 10 내지 40을 가지고, Y는 비닐, 알릴, 아크릴 또는 메타크릴의 열반응성 또는 열경화성 관능기이며, n은 1 내지 3의 정수이다. 상기 유기금속계 커플링제의 사용량은 특별히 한정되지 않지만, 흑연 중량을 기준으로, 0.1~5 중량%의 양이 사용될 수 있다. The organometallic coupling agent

A coupling agent having the formula of may be used, wherein RO is a hydrolyzable group or a substrate reactive group, R is 2 to 10 carbon atoms, and Z is selected from the group consisting of aluminum, silicon, titanium, zinc and zirconium. It is one or more elements, wherein R'is an aliphatic, naphthenic or aromatic thermoplastic functional group, has 10 to 40 carbon atoms, Y is a thermally reactive or thermosetting functional group of vinyl, allyl, acrylic or methacrylic, and n is 1 to It is an integer of 3. The amount of the organometallic coupling agent is not particularly limited, but an amount of 0.1 to 5% by weight based on the weight of graphite may be used.

The use conditions and reaction conditions, such as the addition temperature, the addition method, the addition rate and the stirring rate of the organometallic coupling agent, are not particularly limited, and may be determined from the ordinary knowledge and level of a person skilled in the art.

The prepared MDI and graphite are mixed by stirring for 10 to 30 minutes at RPM 500 to 1500, and then injected into a first container.

On the other hand, the polyol may be a variety of polyols used in the foamed foam, preferably i) in order to increase the strength of the foamed foam, sucrose (Sucrose), such as ethylene oxide (EO), propylene oxide (PO) Polyols with a functional group of 5 to 6 and a hydroxyl value of 400 to 450 mgKOH/g made by polymerizing ene oxide, and ii) ethylene oxide on an amine base such as toluene diamine and ethylene diamine to lower the thermal conductivity and increase the thermal insulation properties of the foam. It is preferable to use a mixture of a polyol having a hydroxyl value of 550 to 650 mgKOH/g made by polymerizing an alkylene oxide such as propylene oxide in a volume ratio of 1:1.

The content of the polyol is preferably 40 to 50% by weight of the total foam composition, and if it is more or less than this, foaming may not be properly performed or the hardness may be too low.

The calcium silicate is added to improve the thermal insulation and sound absorption properties of the foamed foam, and the content is preferably 5 to 10% by weight of the total foam composition, and if it is less than this, the functional effect of calcium silicate may be reduced, If this is exceeded, overall physical properties may deteriorate.

The dispersant serves to help the various ingredients to be uniformly mixed, and various commercially available dispersants may be used. The content is preferably 1 to 5% by weight of the total foam composition, and if it is less than this, the functional effect of the dispersant may be deteriorated, and if it exceeds this, the overall physical properties may deteriorate.

The prepared polyol, calcium silicate, and dispersant are mixed by stirring for 10 to 30 minutes at RPM 500 to 1500, and then injected into a second container.

Meanwhile, in the step of mixing the polyol, calcium silicate, and dispersant, 1 to 10% by weight of phosphoric acid may be additionally added to add plasticity and non-flammability to the foam.

The phosphoric acid may be used alone, but may be used in combination with a phosphorus-containing organic flame retardant in order to increase miscibility and workability with other components, and to enhance plasticity and non-flammability. At this time, the mixing ratio of phosphoric acid and phosphorus-containing flame retardant is preferably about 1 to 2: 1 (w/w). The phosphorus-containing organic flame retardant may be a variety of commercially available phosphorus-containing flame retardants, but preferably tris(2,6-dimethylphenyl)phosphine, tetrakis-(2,6-xylyl)resorcinol bisphosphate, tetra Phenyl resorcinol diphosphate, triphenyl phosphate, phosphazene flame retardant, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-( 2,5-dihydroxynaphthyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide or 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Any one or a mixture of at least two selected from oxide flame retardants may be used.

At this time, in order to solve the problem of decay and deterioration due to the organic flame retardant, it is preferable to add cardanol having an antibacterial effect. The cardanol may be obtained by distilling a cashew nut shell liquid (CNSL) extracted from a cashew nut. The amount of cardanol used is not particularly limited, but 1 to 10% by weight of the weight of the phosphorus-containing organic flame retardant may be used.

On the other hand, in order to further increase the miscibility and stability of the respective components, in the step of mixing the polyol, calcium silicate, and dispersant, it may be additionally added 1 to 3% by weight of cyclodextrin. The cyclodextrin is a cyclic compound composed of a glucose group as a repeating unit. It forms a complex with additives such as calcium silicate or flame retardant, and attracts and immobilizes the additives through hydrogen bonding to the outside, so that it is durable and stable to foamed foam. Can be given.

As the cyclodextrin, various commercially available cyclodextrins may be used, and as an example, 2,3,6-tri-O-naphthoyl-beta-cyclodextrin may be used.

The components A and B prepared as described above can be injected into an empty space and foamed through a high-pressure foamer, thereby finally forming a polyurethane foam in a desired space and performing thermal insulation treatment.

Hereinafter, examples and experimental examples of the present invention will be described. However, the scope of the present invention is not limited to the following preferred embodiments, and those skilled in the art can implement various modified forms of the contents described in the present specification within the scope of the present invention.

<Example 1>

40g of MDI and 5g of graphite were mixed at RPM for 10 minutes and then injected into the first container. Meanwhile, 45 g of polyol, 5 g of calcium silicate, and 5 g of dispersant were mixed at RPM 1000 for 10 minutes and then injected into the second container, and then the materials in the first and second containers were injected and occupied in an empty space through a high pressure foamer. Foamed.

<Example 2>

40g of MDI and 5g of zinc graphite composite were mixed at RPM 1000 for 10 minutes and then injected into the first container. On the other hand, 40 g of polyol, 5 g of calcium silicate, 5 g of dispersant, 2 g of phosphorus, and 3 g of tris(2,6-dimethylphenyl)phosphine were mixed at RPM 1000 for 10 minutes, and then injected into a second container. 2 The materials in the container were injected into the empty space through a high-pressure foamer, and were intersected and foamed.

<Example 3>

40g of MDI and 5g of zinc graphite composite were mixed at RPM 1000 for 10 minutes and then injected into the first container. Meanwhile, 40 g of polyol, 5 g of calcium silicate, 5 g of dispersant, 2 g of phosphorus, and 3 g of tris(2,6-dimethylphenyl)phosphine were mixed at RPM 1000 for 10 minutes and then injected into a second container, and the first container and the agent 2 The materials in the container were injected into the empty space through a high-pressure foamer, and were intersected and foamed.

<Comparative Example>

45 g of MDI was injected into the first container. Meanwhile, 45 g of polyol, 5 g of calcium silicate, and 5 g of dispersant were mixed at RPM 1000 for 10 minutes and then injected into the second container, and then the materials in the first and second containers were injected and occupied in an empty space through a high pressure foamer. Foamed.

<Experimental Example>

The flame retardant performance was evaluated through a heat release rate test after constructing a polyurethane foam test body, and the results are shown in Table 1.

The heat release rate test was performed in accordance with KS F ISO 5660-1:2008. Specifically, after setting and maintaining the radiant heat of the cone heater at about 50 kW/㎡ and the discharge flow rate at about 0024 ㎥/s, the specimen and the specimen holder Was placed on the mass measuring device, the radiant heat shield was removed, heated for 5 minutes, the maximum heat release rate and the total amount of heat emitted were measured, and after the heating was completed, the specimen holder was removed from the mass measuring device and the specimen was observed.

Test Items Details Example 1 Example 2 Example 3 Comparative example Heat release rate Total calories released
(MJ/m2) 2.5 2.2 1.8 5.5 200 kW/m2
Time to exceed (seconds) 0 0 0 5

As can be seen from the above table, it was confirmed that Example 3 of the present invention has the most excellent flame retardant performance.

The present invention is not limited to the specific embodiments and description described above, and any person having ordinary knowledge in the technical field to which the present invention pertains without departing from the gist of the present invention claimed in the claims can implement various modifications. And, such modifications are within the scope of protection of the present invention.

Claims (3)

A component including MDI and graphite; And a component B including polyol, calcium silicate and a dispersant;
The content of each component is 40 to 50% by weight of polyol, 35 to 45% by weight of MDI, 5 to 10% by weight of graphite, 5 to 10% by weight of calcium silicate and 1 to 5% by weight of dispersant,
The graphite is a composite with zinc, and the composite comprises dispersing an organometallic coupling agent and graphite in an aqueous medium; Adding zinc chloride or zinc iodide to the dispersion and then drying to obtain a zinc/coupling agent/graphite composite; And it is produced through the step of firing the dried composite;
The organometallic coupling agent

As a coupling agent having the formula of, RO is a hydrolyzable group or a substrate reactive group, R is 2 to 10 carbon atoms, and Z is at least one element selected from the group consisting of aluminum, silicon, titanium, zinc and zirconium, R'is an aliphatic, naphthenic, or aromatic thermoplastic functional group, having 10 to 40 carbon atoms, Y is a thermally reactive or thermosetting functional group of vinyl, allyl, acrylic or methacrylic, n is an integer of 1 to 3, wherein A kit for producing polyurethane foam, characterized in that the amount of the organometallic coupling agent is 0.1 to 5% by weight compared to graphite. delete delete