KR20100100951A - Process for production of hard polyurethane foam - Google Patents
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- KR20100100951A KR20100100951A KR1020107015017A KR20107015017A KR20100100951A KR 20100100951 A KR20100100951 A KR 20100100951A KR 1020107015017 A KR1020107015017 A KR 1020107015017A KR 20107015017 A KR20107015017 A KR 20107015017A KR 20100100951 A KR20100100951 A KR 20100100951A
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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- C08G18/00—Polymeric products of isocyanates or isothiocyanates
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- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
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- C08G18/6677—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
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- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
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- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
- C08J2375/08—Polyurethanes from polyethers
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Abstract
본 발명은, 경화특성이 우수하고, 단시간에 탈형 성형 가능한, 시클로펜탄에 의해 발포된 후물 단열재용 경질 폴리우레탄폼의 제조 방법을 제공하는 것을 과제로 하며, 폴리이소시아네이트(a)와 폴리올(b)을, 촉매(c), 발포제(d)의 존재하에서 반응·발포시키는 후물 단열재용 경질 폴리우레탄폼의 제조 방법에 있어서, 폴리이소시아네이트(a)가, 폴리머릭 MDI(a1-1)와 측쇄 알킬기를 가지는 저분자 폴리올(a1-2)을 반응시켜 생성한 이소시아네이트기 함유 프리폴리머(a1) 및 정포제(a2)를 함유하며, 폴리올(b)이, 4종류의 폴리에테르폴리올(b1∼b4)을 함유하고, 촉매(c)가, 우레탄화 촉매(c1)와 3량화 촉매(c2)를 함유하며, 발포제(d)가 시클로펜탄(d1) 및 물(d2)을 병용함으로써 상기 과제를 해결한다.It is an object of the present invention to provide a method for producing a rigid polyurethane foam for after-heat insulation material foamed with cyclopentane, which is excellent in curing properties and capable of demolding in a short time, and is a polyisocyanate (a) and a polyol (b). In the method for producing a rigid polyurethane foam for a material heat insulating material which reacts and foams in the presence of a catalyst (c) and a blowing agent (d), the polyisocyanate (a) is a polymeric MDI (a1-1) and a branched alkyl group. The eggplant contains an isocyanate group-containing prepolymer (a1) and a foam stabilizer (a2) formed by reacting a low molecular polyol (a1-2), and the polyol (b) contains four kinds of polyether polyols (b1 to b4). The catalyst (c) contains a urethanization catalyst (c1) and a trimerization catalyst (c2), and the blowing agent (d) solves the above problems by using cyclopentane (d1) and water (d2) in combination.
Description
본 발명은, 경화특성(curing property)이 우수하며, 단시간에 성형 가능한 후물용(厚物用)의 시클로펜탄에 의해 발포된 경질 폴리우레탄폼의 제조 방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a rigid polyurethane foam foamed with cyclopentane for thick materials which is excellent in curing properties and can be molded in a short time.
경질 폴리우레탄폼은, 단열 성능, 치수 안정성 및 시공성이 우수하기 때문에, 냉장고, 냉동 창고, 건축 재료 등의 단열재로서, 또한 스프레이 용도로서 광범위하게 사용되고 있다. 종래, 경질 폴리우레탄폼의 발포제로서 낮은 열전도율과 바람직한 비점을 가지는 트리클로로플루오로메탄(이하, "CFC-11"로 기재함)이 주로 사용되었다. 그러나, 클로로플루오로카본류(이하, "CFC류" 로 기재함)는, 분자 중에 염소 원자를 포함하고, 또한 매우 안정적인 분자이므로 확산 효과에 의해 오존층까지 도달하고, 오존과 반응하여 지구의 오존층을 파괴하는 물질이라는 설이 대두되어, 이미 1995년 말에, CFC류의 사용은 전면적으로 폐지되어 있다. 현재, 경질 폴리우레탄폼의 발포제로서는, 그 대체물인 하이드로클로로플루오로카본류(이하, "HCFC류"로 기재함)가 사용되고, 특히 단열 성능이 요구되는 것에 대해서는, HCFC류 중에서도 낮은 열전도율을 가지는 HCFC-141b의 사용이 주류가 되어 있다.Since rigid polyurethane foam is excellent in heat insulation performance, dimensional stability, and workability, it is used extensively as a heat insulating material, such as a refrigerator, a freezer, a building material, and a spray use. Conventionally, trichlorofluoromethane (hereinafter referred to as "CFC-11") having low thermal conductivity and a preferable boiling point has been mainly used as a blowing agent of rigid polyurethane foam. However, chlorofluorocarbons (hereinafter referred to as "CFCs") contain chlorine atoms in the molecule and are very stable molecules, reaching the ozone layer by the diffusion effect, and reacting with ozone to destroy the earth's ozone layer. The substance has emerged, and by the end of 1995, the use of CFCs has been completely abolished. Currently, as a blowing agent for rigid polyurethane foams, hydrochlorofluorocarbons (hereinafter referred to as "HCFCs"), which are substitutes thereof, are used. Especially for those requiring heat insulation performance, HCFC- having low thermal conductivity among HCFCs is required. The use of 141b has become mainstream.
일반적으로, 단열용도의 경질 폴리우레탄폼은, 셀 내에 발포제가 봉입된 독립 기포 구조를 취하고 있다. 그러므로 비점이 상온 이상(25℃ 이상)인 발포제를 사용한 경우, 상온 또는 저온 하에서, 셀 내에 봉입된 발포제의 액화에 기인한 셀 내 압력의 저하가 일어난다. 이 현상은 발포제 고유의 증기압에 의한 것이며, 그 결과로서 경질 폴리우레탄폼은 수축한다. 즉, 이들 상온 이상 (25℃ 이상)의 비점을 가지는 발포제를 사용한 발포 기술을 실용화하는데 있어서 가장 곤란한 문제는, 상온 이하에서의 경질 폴리우레탄폼 수축의 회피, 즉 양호한 치수 안정성을 유지시키는 것이다.In general, rigid polyurethane foam for thermal insulation has an independent bubble structure in which a foaming agent is enclosed in a cell. Therefore, when a blowing agent having a boiling point above room temperature (above 25 ° C) is used, a decrease in the pressure in the cell due to liquefaction of the blowing agent enclosed in the cell occurs at room temperature or at a low temperature. This phenomenon is due to the vapor pressure inherent to the blowing agent, and as a result, the rigid polyurethane foam shrinks. That is, the most difficult problem in practical use of the foaming technique using the foaming agent having the boiling point above these room temperature (25 degreeC or more) is the avoidance of the shrinkage of rigid polyurethane foam below normal temperature, ie, maintaining good dimensional stability.
생산 비용 삭감 및 에너지 절약과 결부되는 과제로서, 경질 폴리우레탄폼의 저밀도화가 요구되고 있다. 산업상의 이용 가치를 손상시키지 않고 이 요구에 부응하기 위해서는, 상온 이하에서의 수축이 보다 적으며 저밀도화 가능한 경질 폴리우레탄폼의 제조법의 확립이 필수적이 된다. 또한, 지구 환경/오존층 보호의 요구가 거세어지고 있는 중에, HCFC류도 분자 중에 염소 분자를 포함하므로 ODP가 제로("0")가 아니고, 2004년부터 규제의 대상으로 되는 것이 이미 정해져 있다. HCFC류의 대체 화합물로서는, 하이드로플루오로카본류(이하, "HFC류"로 기재함), 또한 시클로펜탄(이하, "CP"로 기재함)으로 대표되는 하이드로카본(이하, "HC"로 기재함)류 등의 ODP가 제로인 발포제가 검토되고 있다. 그러나, HFC류 중에는 1,1,1,2-테트라플루오로에탄(비점: -26.2℃), 1,1-디플루오로에탄(비점: -24.2℃), 1,1,1,2,2-펜타플루오로에탄(비점: -48.5℃) 등과 같이 비점이 0℃ 이하인 화합물도 많으며, 공업상 이들을 발포제로서 취급하려면 고압 가스 대응과 같은 설비 대응이 필요하다.As a problem associated with a reduction in production cost and energy saving, a reduction in the density of rigid polyurethane foams is required. In order to meet this demand without compromising industrial utility value, it is essential to establish a manufacturing method of a rigid polyurethane foam which is less shrinkable at room temperature or less and can be reduced. In addition, while the demand for protection of the global environment / ozone layer is increasing, since HCFCs also contain chlorine molecules in their molecules, ODP is not zero (“0”) and has already been regulated since 2004. As an alternative compound of HCFCs, hydrocarbons represented by hydrofluorocarbons (hereinafter referred to as "HFCs") and cyclopentane (hereinafter referred to as "CP") (hereinafter referred to as "HC") are described. Foaming agents having an ODP of 0, etc., are being studied. However, among HFCs, 1,1,1,2-tetrafluoroethane (boiling point: -26.2 ° C), 1,1-difluoroethane (boiling point: -24.2 ° C), 1,1,1,2,2 Many compounds having a boiling point of 0 ° C. or lower, such as pentafluoroethane (boiling point: −48.5 ° C.) and the like, require industrial equipment to be treated such as high pressure gas to treat them as blowing agents.
HC류를 발포제로 만들 경우, 방폭 설비 대응으로 할 필요가 있지만, 레진프리믹스(Resin Premix)는 액상(液狀)으로 비교적 취급하기 쉬운 이점이 있다. 특히, HC류 중에서 열전도율이 낮은 것으로서 CP를 예로 들 수 있다. 또한, 발포제로서 사용하기에 적합한 비점을 가지는 것으로서는 탄소수 5∼6의 HC류가 있다. CP 또는 HC류를 발포제 중의 성분으로서 사용한 예로서, 특허 문헌 1이 있고, 또한 에스테르폴리올을 사용함으로써, 양호한 제반 물성을 유지한 상태에서 특히 CFC-11 삭감 발포 기술과 동등한 정도 이하의 열전도율을 실현한 예로서, 비특허 문헌 1이 알려져 있다. 그러나, CP의 비점은 49.3℃이며, 상기 산업상의 저밀도화 요구에 부응하기 위해서는, 역시 상온 이하에서 수축되는 문제점을 피할 수 없게 된다.When HCs are used as foaming agents, it is necessary to be compatible with explosion-proof equipment, but Resin Premix has an advantage of being relatively easy to handle as a liquid. In particular, CP is exemplified as a low thermal conductivity among HCs. In addition, HCs having 5 to 6 carbon atoms have a boiling point suitable for use as a blowing agent. As an example of using CP or HC as a component in the foaming agent, Patent Document 1 discloses, and by using ester polyol, in particular, thermal conductivity of less than or equal to that of CFC-11 reduced foaming technology is realized while maintaining good physical properties. As an example, Non Patent Literature 1 is known. However, the boiling point of CP is 49.3 ° C, and in order to meet the industrial demand for lowering density, the problem of shrinking below room temperature is inevitable.
전술한 바와 같은 문제를 해결하기 위하여, 특허 문헌 2에 관한 기술이 제안되어 있다. 그러나, 특허 문헌 2의 기술에서는, 폴리올 혼합물과 시클로펜탄과의 상용성(相溶性)이 좋지못하므로, 탁해지거나 2층 분리가 생기기 쉽고, 나아가서는 균일한 폼을 얻기 곤란한 문제점이 있는 것을 알았다.In order to solve the problem as mentioned above, the technique regarding patent document 2 is proposed. However, in the technique of Patent Document 2, since the compatibility between the polyol mixture and cyclopentane is not good, it has been found that turbidity and two-layer separation are likely to occur, and further, it is difficult to obtain a uniform foam.
또한, 후물 단열재(두께 100mm 이상)에서의 경질 폴리우레탄폼에 있어서는, 경화특성 부족으로 인하여 폼 내부에 분열이 생기는 경우가 많다. 이 점을 개선하기 위해서는, 성형 시간을 길게 하는 등의 방법이 있지만, 이와 같은 방법은 생산성의 저하로 이어지므로, 근본적인 해결이 요구되고 있다. 그리고, 이후 본원에 있어서 「후물 단열재」란, 두께 100mm 이상의 단열재를 말하기로 하고, 「두께」란, 목적으로 하는 단열 방향의 거리를 의미하는 것으로 한다.In addition, in a rigid polyurethane foam in a thick heat insulating material (thickness of 100 mm or more), breakage is often generated inside the foam due to lack of curing characteristics. In order to improve this point, there exist methods, such as lengthening molding time, but since such a method leads to the fall of productivity, the fundamental solution is calculated | required. In the present application, the term "thick material heat insulating material" shall refer to a heat insulating material having a thickness of 100 mm or more, and "thickness" shall mean a distance in the target heat insulating direction.
본 발명은, 폴리올과 시클로펜탄과의 상용성이나, 경화특성이 뛰어나기 때문에 단시간에 성형 가능한, 시클로펜탄에 의해 발포된 후물 단열재용 경질 폴리우레탄폼의 제조 방법의 제공을 목적으로 한다.An object of the present invention is to provide a method for producing a rigid polyurethane foam for a heat insulating material foamed with cyclopentane, which can be molded in a short time because of excellent compatibility with polyols and cyclopentane and curing properties.
즉 본 발명은,That is, the present invention,
폴리이소시아네이트(A)와 폴리올(B)을, 촉매(C), 발포제(D)의 존재하에서 반응·발포시키는 후물 단열재용 경질 폴리우레탄폼의 제조 방법에 있어서,In the manufacturing method of the rigid polyurethane foam for after-heat insulation materials which makes polyisocyanate (A) and polyol (B) react and foam in presence of a catalyst (C) and a foaming agent (D),
폴리이소시아네이트(A)가, 폴리머릭 MDI(A1-1)와, 측쇄 알킬기를 가지는 저분자 폴리올(A1-2)을 반응시켜 생성한 이소시아네이트기 함유 프리폴리머(A1) 및 정포제(A2)를 함유하고,The polyisocyanate (A) contains an isocyanate group-containing prepolymer (A1) and a foam stabilizer (A2) produced by reacting a polymeric MDI (A1-1) with a low molecular polyol (A1-2) having a side chain alkyl group,
폴리올(B)이, 이하의 폴리올(B1∼B4)를 함유하고,The polyol (B) contains the following polyols (B1 to B4),
촉매(C)가, 우레탄화 촉매(C1)와 3량화 촉매(C2)를 함유하고,Catalyst (C) contains a urethanization catalyst (C1) and a trimerization catalyst (C2),
발포제(D)가 시클로펜탄(D1) 및 물(D2)을 병용하는 것을 특징으로 하는, 후물 단열재용 경질 폴리우레탄폼의 제조 방법을 제공한다.The foaming agent (D) provides cyclopentane (D1) and water (D2) together, The manufacturing method of the rigid polyurethane foam for thick insulation is provided.
폴리올(B1):Polyol (B1):
슈크로스를 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어지고, 평균 관능기수 = 3∼6, 수산기가 = 300∼600 mgKOH/g인 폴리에테르 폴리올Polyether polyol obtained by addition of propylene oxide to an initiator having sucrose as a main component, and having an average number of functional groups = 3 to 6 and a hydroxyl value = 300 to 600 mgKOH / g
폴리올(B2):Polyol (B2):
소르비톨을 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어지고, 평균 관능기수 = 3∼6, 수산기가 = 300∼600 mgKOH/g인 폴리에테르 폴리올Polyether polyol obtained by addition of propylene oxide to an initiator containing sorbitol as a main component and having an average number of functional groups = 3 to 6 and a hydroxyl group = 300 to 600 mgKOH / g
폴리올(B3):Polyol (B3):
글리세린을 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어지고, 평균 관능기수 = 2∼4, 수산기가 = 1000∼1500 mgKOH/g인 폴리에테르 폴리올Polyether polyol which is obtained by addition of propylene oxide to an initiator containing glycerin as a main component and has an average number of functional groups = 2 to 4 and a hydroxyl value = 1000 to 1500 mgKOH / g.
폴리올(B4):Polyol (B4):
에틸렌디아민을 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어지고, 평균 관능기수 = 3∼5, 수산기가 = 400∼800 mgKOH/g인 폴리에테르 폴리올Polyether polyol which is obtained by addition of propylene oxide to an initiator having ethylenediamine as a main component and has an average number of functional groups = 3 to 5 and a hydroxyl group = 400 to 800 mgKOH / g.
본 발명에 의해, 경화특성이 우수하며, 단시간에 성형 가능한 후물용 시클로펜탄에 의해 발포된 후물 단열재용 경질 폴리우레탄폼의 제조가 가능하게 되었다.According to the present invention, it is possible to manufacture a rigid polyurethane foam for a thick heat insulating material foamed with cyclopentane for thick material, which is excellent in curing characteristics and can be molded in a short time.
본 발명에 사용되는 폴리이소시아네이트(A)는, 폴리머릭 MDI(A1-1)와, 측쇄 알킬기를 가지는 저분자 폴리올(A1-2)을 반응시켜 생성한 이소시아네이트기 함유 프리폴리머(A1) 및 정포제(A2)를 함유한다.The polyisocyanate (A) used in the present invention is an isocyanate group-containing prepolymer (A1) and a foam stabilizer (A2) produced by reacting a polymeric MDI (A1-1) with a low molecular polyol (A1-2) having a side chain alkyl group. ).
폴리머릭 MDI(A1-1)는, 아닐린과 포르말린과의 축합 반응에 의해 얻어지는 축합 혼합물(폴리아민)을 포스겐화 등에 의해 아미노기를 이소시아네이트기로 전화(轉化)하여, 필요에 따라 이성화함으로써 얻어지는, 축합도가 상이한 유기 이소시아네이트 화합물의 혼합물을 의미하고, 축합 시의 원료 조성비나 반응 조건을 변경함으로써, 최종적으로 얻어지는 폴리머릭 MDI의 조성을 변화시킬 수 있다. 본 발명에 사용되는 폴리머릭 MDI는, 이소시아네이트기로의 전화 후의 반응액, 또는 반응액으로부터 용매를 제거하거나 또는 일부 MDI를 유출 분리한 유출액, 반응 조건이나 분리 조건 등이 상이한 여러 종류의 혼합물이라도 된다. 또한, 이소시아네이트기의 일부를 뷰렛, 알로파네이트, 카르보디이미드, 옥사졸리돈, 아미드, 이미드 등으로 변성시킨 것이라도 된다.Polymeric MDI (A1-1) has a degree of condensation obtained by converting a condensation mixture (polyamine) obtained by a condensation reaction between aniline and formalin into an isocyanate group by phosgenation or the like, and isomerization as necessary. By mixing a mixture of different organic isocyanate compounds and changing the raw material composition ratio and reaction conditions during condensation, the composition of the finally obtained polymeric MDI can be changed. The polymeric MDI used in the present invention may be a reaction solution after conversion to an isocyanate group, or a mixture of different kinds of distillates obtained by removing a solvent from the reaction solution or distilling some MDI out, reaction conditions or separation conditions. In addition, a part of isocyanate groups may be modified by biuret, allophanate, carbodiimide, oxazolidone, amide, imide, or the like.
폴리머릭 MDI(A1-1)의 평균 관능기수는 2.3 이상이며, 관능기수가 2.3∼3.1이 바람직하다. 이소시아네이트 함량은, 28∼33 질량%이며, 28.5∼32.5 질량%가 바람직하다. 또한, 점성도(25℃)는 50∼500 mPa·s가 바람직하고, 100∼300 mPa·s가 특히 바람직하다.The average number of functional groups of the polymeric MDI (A1-1) is 2.3 or more, and the number of functional groups is preferably 2.3 to 3.1. Isocyanate content is 28-33 mass%, and 28.5-32.5 mass% is preferable. Moreover, as for viscosity (25 degreeC), 50-500 mPa * s is preferable and 100-300 mPa * s is especially preferable.
폴리머릭 MDI(A1-1) 중에는, 1분자 중에 벤젠환 및 이소시아네이트기를 각각 2개 가지는 디페닐메탄디이소시아네이트(MDI), 이른바 2핵체로 일컬어지고 있는 성분을 함유한다. MDI를 구성하는 이성체는, 2,2'-디페닐메탄디이소시아네이트(이후, 2,2'-MDI로 약칭함), 2,4'-디페닐메탄디이소시아네이트(이후, 2,4'-MDI로 약칭함), 4,4'-디페닐메탄디이소시아네이트(이후, 4,4'-MDI로 약칭함)의 3종류이다. MDI의 이성체 구성비는 특별히 한정되지 않지만, 4,4'-MDI 함유량이 70 질량% 이상, 90∼99.9 질량%인 것이, 얻어지는 폼의 강도가 향상되므로 바람직하다. 그리고, 폴리머릭 MDI의 MDI 함유량이나, MDI의 이성체 구성비는, GPC나 가스크로마토그래피(이하, GC로 약칭함)에 의해 얻어지는 각 피크의 면적 백분율에 기초하여 검량선으로부터 구할 수 있다.The polymeric MDI (A1-1) contains the component called diphenylmethane diisocyanate (MDI) which has two benzene rings and two isocyanate groups in 1 molecule, so-called binuclear bodies. Isomers constituting MDI include 2,2'-diphenylmethane diisocyanate (hereinafter abbreviated as 2,2'-MDI), 2,4'-diphenylmethane diisocyanate (hereinafter, 2,4'-MDI). And 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as 4,4'-MDI). Although the isomer constitution ratio of MDI is not specifically limited, It is preferable that 4,4'-MDI content is 70 mass% or more and 90-99.9 mass%, since the intensity | strength of the foam obtained is improved. The MDI content of the polymeric MDI and the isomer composition ratio of the MDI can be obtained from the calibration curve based on the area percentage of each peak obtained by GPC or gas chromatography (hereinafter, abbreviated as GC).
본 발명에 사용되는 폴리머릭 MDI(A1-1)는, 겔투과 크로마토그래피(이하, GPC로 약칭함)에서의 2핵체(1분자 중에 벤젠환을 2개 가지는 것) 성분의 피크 면적비가 20∼70 %로 되는 것이며, 25∼65 %로 되는 것이 바람직하다. 2핵체의 피크 면적비가 70%를 초과하면, 얻어지는 경질 폴리우레탄폼의 강도가 저하되고, 또한 부서지기 쉽다. 한편 20% 미만의 경우에는, 얻어지는 폴리이소시아네이트의 점성도가 높아지고, 금형에 대한 충전성이 저하되기 쉽다.As for polymeric MDI (A1-1) used for this invention, the peak area ratio of the binuclear body (thing which has two benzene rings in 1 molecule) component in gel permeation chromatography (it abbreviates as GPC hereafter) is 20- It becomes 70%, and it is preferable to become 25 to 65%. When the peak area ratio of the binary nucleus exceeds 70%, the strength of the resulting rigid polyurethane foam is lowered and easily broken. On the other hand, when it is less than 20%, the viscosity of the polyisocyanate obtained becomes high and the filling property to a metal mold | die will fall easily.
본 발명에서는 필요에 따라 전술한 폴리머릭 MDI 이외의 폴리이소시아네이트를 사용할 수 있다. 예를 들면, MDI의 이소시아누레이트 변성물, 우레톤이민 변성물, 알로파네이트 변성물 등이 있다. 또한, 2,4-톨릴렌디이소시아네이트, 2,6-톨릴렌디이소시아네이트, 크실렌-1,4-디이소시아네이트, 크실렌-1,3-디이소시아네이트, 테트라메틸크실렌디이소시아네이트, m-페닐렌디이소시아네이트, p-페닐렌디이소시아네이트 등의 방향족 디이소시아네이트, 테트라메틸렌디이소시아네이트, 헥사메틸렌디이소시아네이트, 3-메틸-1,5-펜탄디이소시아네이트, 리진디이소시아네이트 등의 지방족 디이소시아네이트, 이소포론디이소시아네이트, 수소 첨가 톨릴렌디이소시아네이트, 수소 첨가 크실렌디이소시아네이트, 수소 첨가 디페닐메탄디이소시아네이트 등의 지환족 디이소시아네이트 등을 예로 들 수 있다. 또한, 이들 폴리머릭체나 우레탄화물, 우레아화물, 알로파네이트화물, 뷰렛화물, 카르보디이미드화물, 우레톤이민화물, 우레트디온화물, 이소시아누레이트화물 등을 예로 들 수 있고, 또한 이들의 2종 이상의 혼합물을 예로 들 수 있다.In the present invention, polyisocyanates other than the polymeric MDI mentioned above can be used as needed. For example, isocyanurate modified substance of MDI, uretonimine modified substance, allophanate modified substance, etc. are mentioned. Moreover, 2, 4- tolylene diisocyanate, 2, 6- tolylene diisocyanate, xylene-1, 4- diisocyanate, xylene-1, 3- diisocyanate, tetramethyl xylene diisocyanate, m-phenylene diisocyanate, p- Aromatic diisocyanates such as phenylene diisocyanate, aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 3-methyl-1,5-pentane diisocyanate and lysine diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate And alicyclic diisocyanate, such as hydrogenated xylene diisocyanate and hydrogenated diphenylmethane diisocyanate, etc. are mentioned. Moreover, these polymers, urethane, urea, allophanate, biuret, carbodiimide, uretonimide, uretdione, isocyanurate and the like are exemplified. 2 or more types of mixtures are mentioned.
본 발명에 사용되는 저분자 폴리올(A1-2)은, 측쇄 알킬기를 가지는 저분자 폴리올이다. 폴리머릭 MDI(A1-1)를 측쇄 알킬기를 가지는 저분자 폴리올(A1-2)로 우레탄 변성함으로써, 이소시아네이트기 함유 프리폴리머(A1)와 정포제(A2)와의 상용성을 개선할 수 있다. 그 결과, 시클로펜탄과의 상용성이 좋지못한 정포제(A2)를 폴리올액에 배합해 둘 필요가 없어지고, 시클로펜탄을 배합한 폴리올액의 안정성이 향상됨으로써, 균일한 폼을 얻을 수 있게 된다. 또한, 경화특성 개선에도 기여하는 것을 알았다.The low molecular polyol (A1-2) used for this invention is a low molecular polyol which has a branched alkyl group. By urethane-modifying polymeric MDI (A1-1) with the low molecular polyol (A1-2) which has a side chain alkyl group, compatibility of an isocyanate group containing prepolymer (A1) and a foam stabilizer (A2) can be improved. As a result, it is not necessary to mix | blend the foam stabilizer (A2) which is incompatible with cyclopentane with a polyol liquid, and the stability of the polyol liquid which mix | blended cyclopentane improves, and a uniform foam can be obtained. . Moreover, it turned out that it contributes also to the improvement of hardening characteristic.
이와 같은 측쇄 알킬기를 가지는 저분자 폴리올(A1-2)로서는, 1,2-프로판디올, 1,3-부탄디올, 네오펜틸글리콜, 3-메틸-1,5-프로판디올, 디프로필렌글리콜, 2-메틸-1,3-프로판디올, 수소 첨가 비스페놀A, 2,2-디에틸-1,3-프로판디올, 2,4-디에틸-1,5-펜탄디올, 2,2-디메틸올헵탄 등을 예로 들 수 있다. 본 발명에 있어서는, 분자량이 작은 것일수록, 프리폴리머에 측쇄 알킬기를 효율적으로 도입할 수 있으므로, 1,2-프로판디올이 가장 바람직하다.As a low molecular polyol (A1-2) which has such a side chain alkyl group, 1, 2- propanediol, 1, 3- butanediol, neopentyl glycol, 3-methyl- 1, 5- propanediol, dipropylene glycol, 2-methyl -1,3-propanediol, hydrogenated bisphenol A, 2,2-diethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 2,2-dimethylolheptane and the like For example. In the present invention, the smaller the molecular weight, the more efficiently the side chain alkyl group can be introduced into the prepolymer, so that 1,2-propanediol is most preferred.
본 발명에 사용되는 폴리이소시아네이트(A)는, 전술한 폴리머릭 MDI(A1-1)와 측쇄 알킬기를 가지는 저분자 폴리올(A1-2)을 40∼100 ℃에서 반응시켜, 이소시아네이트기 함유 프리폴리머(A1)를 합성하고, 후술하는 정포제(A2)를 첨가함으로써 얻어진다. 폴리머릭 MDI(A1-1)와 측쇄 알킬기를 가지는 저분자 폴리올(A1-2)의 비율은, 이소시아네이트기(NCO)와 수산기(OH)의 몰비로 NCO/OH = 50/1∼1000/1이 바람직하다. OH가 지나치게 적은 경우에는, 경화특성 향상의 효과를 바랄 수 없다. OH가 지나치게 많은 경우에는, 얻어지는 폴리이소시아네이트의 점성도가 높아지므로 실제 제조 시의 송액이 곤란하게 된다. 이와 같이 하여 얻어진 폴리이소시아네이트(A)의 이소시아네이트 함량은 28∼31 질량%가 바람직하고, 29∼30.5 질량%가 특히 바람직하다.The polyisocyanate (A) used for this invention reacts the above-mentioned polymeric MDI (A1-1) and the low molecular polyol (A1-2) which has a side chain alkyl group at 40-100 degreeC, and isocyanate group containing prepolymer (A1). It synthesize | combines and is obtained by adding the foam stabilizer (A2) mentioned later. As for the ratio of polymeric MDI (A1-1) and the low molecular polyol (A1-2) which has a branched alkyl group, NCO / OH = 50/1-1000/1 is preferable in molar ratio of an isocyanate group (NCO) and a hydroxyl group (OH). Do. When there is too little OH, the effect of hardening characteristic improvement cannot be desired. When there is too much OH, since the viscosity of the polyisocyanate obtained becomes high, the liquid feeding at the time of manufacture becomes difficult. 28-31 mass% is preferable, and, as for the isocyanate content of the polyisocyanate (A) obtained in this way, 29-30.5 mass% is especially preferable.
본 발명에 사용되는 정포제(A2)로서는, 공지의 실리콘계 계면활성제를 예로 들 수 있으며, 도오레·다우코닝사 제품인 L-5340, L-5420, L-5421, L-5740, L-580, SZ-1142, SZ-1642, SZ-1605, SZ-1649, SZ-1675, SH-190, SH-192, SH-193, SF-2945F, SF-2940F, SF-2936F, SF-2938F, SRX-294A, 신에쓰화학공업사 제품인 F-305, F-341, F-343, F-374, F-345, F-348, 골드슈미트사 제품인 B-8404, B-8407, B-8465, B-8444, B-8467, B-8433, B-8466, B-8870, B-8450 등이 있다. 정포제(A2)의 사용량은, 폴리올(B)에 대하여, 0.1∼5 질량%가 되는 양이 적합하다.As a foam stabilizer (A2) used for this invention, a well-known silicone type surfactant is mentioned, For example, L-5340, L-5420, L-5421, L-5740, L-580, and SZ by Toray Dow Corning -1142, SZ-1642, SZ-1605, SZ-1649, SZ-1675, SH-190, SH-192, SH-193, SF-2945F, SF-2940F, SF-2936F, SF-2938F, SRX-294A , Shin-Etsu Chemical Co., Ltd. F-305, F-341, F-343, F-374, F-345, F-348, Gold Schmidt's B-8404, B-8407, B-8465, B-8444, B-8467, B-8433, B-8466, B-8870, and B-8450. As for the usage-amount of foam stabilizer (A2), the quantity used as 0.1-5 mass% with respect to a polyol (B) is suitable.
본 발명에 사용되는 폴리이소시아네이트(A)에는, 필요에 따라 산화 방지제, 자외선 흡수제, 난연제, 가소제, 안료·염료·항균제·항곰팡이제 등의 각종 첨가제나 조제를 첨가할 수 있다.To the polyisocyanate (A) used in the present invention, various additives and preparations such as antioxidants, ultraviolet absorbers, flame retardants, plasticizers, pigments, dyes, antibacterial agents and antifungal agents can be added as necessary.
본 발명에 사용되는 폴리올(B)은, 이하의 폴리올(B1∼B4)를 함유하는 것이다.The polyol (B) used for this invention contains the following polyols (B1-B4).
폴리올(B1):Polyol (B1):
슈크로스를 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어지고, 평균 관능기수 = 3∼6, 수산기가 = 300∼600 mgKOH/g인 폴리에테르 폴리올Polyether polyol obtained by addition of propylene oxide to an initiator having sucrose as a main component, and having an average number of functional groups = 3 to 6 and a hydroxyl value = 300 to 600 mgKOH / g
폴리올(B2):Polyol (B2):
소르비톨을 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어지고, 평균 관능기수 = 3∼6, 수산기가 = 300∼600 mgKOH/g인 폴리에테르 폴리올Polyether polyol obtained by addition of propylene oxide to an initiator containing sorbitol as a main component and having an average number of functional groups = 3 to 6 and a hydroxyl group = 300 to 600 mgKOH / g
폴리올(B3):Polyol (B3):
글리세린을 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어지고, 평균 관능기수 = 2∼4, 수산기가 = 1000∼1500 mgKOH/g인 폴리에테르 폴리올Polyether polyol which is obtained by addition of propylene oxide to an initiator containing glycerin as a main component and has an average number of functional groups = 2 to 4 and a hydroxyl value = 1000 to 1500 mgKOH / g.
폴리올(B4):Polyol (B4):
에틸렌 디아민을 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어지고, 평균 관능기수 = 3∼5, 수산기가 = 400∼800 mgKOH/g인 폴리에테르 폴리올Polyether polyol which is obtained by addition of propylene oxide to an initiator having ethylene diamine as a main component and has an average number of functional groups = 3 to 5 and a hydroxyl group = 400 to 800 mgKOH / g.
각 폴리올의 가장 바람직한 질량 배합비는 (B1):(B2):(B3):(B4) = 60:20:15:5이다.The most preferable mass compounding ratio of each polyol is (B1) :( B2) :( B3) :( B4) = 60: 20: 15: 5.
본 발명에 사용되는 촉매(C)는, 우레탄화 촉매(C1)와 3량화 촉매(C2)를 함유하는 것을 특징으로 한다. 우레탄화 촉매(C1)로서는, N-메틸이미다졸, 트리메틸아미노에틸피페라진, 트리프로필아민, 테트라메틸헥사메틸렌디아민, 트리에틸렌디아민, 트리에틸아민, N-메틸모르폴린, 디메틸시클로헥실아민, 디부틸주석디아세테이트, 디부틸주석디라우레이트 등의 주석 화합물, 아세틸아세톤 금속염 등의 금속착화합물(metallic complex compound) 등을 예로 들 수 있다. 3량화 촉매(C2)로서는, 2,4,6-트리스(디메틸아미노메틸)페놀, 1,3,5-트리스(디메틸아미노프로필)헥사하이드로-s-트리아진 등의 트리아진류, 2,4-비스(디메틸아미노메틸)페놀, 2-에틸헥산산 칼륨, 2-에틸헥산산 나트륨, 아세트산 칼륨, 아세트산 나트륨, 2-에틸아지리딘 등의 아지리딘류 등의 아민계 화합물, 3급 아민의 카르복시산염 등의 제4급 암모늄 화합물, 디아자비시클로운데센, 나프텐산 납, 옥틸산 납 등의 납화합물, 나트륨메톡사이드 등의 알콜레이트 화합물, 칼륨페녹사이드 등의 페놀레이트 화합물 등을 예로 들 수 있다. 이들(C1) 및 (C2)는, 1종 또는 2종 이상 병용하여 사용할 수 있다. 전체 촉매(C)의 사용량은, 폴리올에 대하여, 0.01∼15 질량%가 되는 양이 적합하다.Catalyst (C) used in the present invention is characterized by containing a urethanization catalyst (C1) and a trimerization catalyst (C2). Examples of the urethanization catalyst (C1) include N-methylimidazole, trimethylaminoethylpiperazine, tripropylamine, tetramethylhexamethylenediamine, triethylenediamine, triethylamine, N-methylmorpholine, dimethylcyclohexylamine, And tin compounds such as dibutyltin diacetate and dibutyltin dilaurate, and metal complex compounds such as acetylacetone metal salts. Examples of the trimerization catalyst (C2) include triazines such as 2,4,6-tris (dimethylaminomethyl) phenol, 1,3,5-tris (dimethylaminopropyl) hexahydro-s-triazine, and 2,4- Amine compounds such as aziridine such as bis (dimethylaminomethyl) phenol, potassium 2-ethylhexanoate, sodium 2-ethylhexanoate, potassium acetate, sodium acetate, 2-ethylaziridine, and carboxylates of tertiary amines; And quaternary ammonium compounds, diazabicycloundecene, lead naphthenate, lead octylate and the like, alcoholate compounds such as sodium methoxide, and phenolate compounds such as potassium phenoxide. These (C1) and (C2) can be used 1 type or in combination or 2 or more types. As for the usage-amount of all the catalysts (C), the quantity used as 0.01-15 mass% with respect to a polyol is suitable.
또한, 반응 촉진을 위한 조촉매로서, 예를 들면 에틸렌카보네이트, 프로필렌카보네이트 등의 카보네이트 화합물을 사용할 수 있다.Moreover, as a promoter for reaction promotion, carbonate compounds, such as ethylene carbonate and a propylene carbonate, can be used, for example.
발포제(D)는, 시클로펜탄 및 물이다. 발포제가 시클로펜탄으로만 되어 있는 경우에는, 얻어지는 폼이 수축되기 쉽다. 발포제의 사용량은, 폴리올에 대하여 시클로펜탄이 0.1∼30 질량%, 물이 0.1∼3 질량%이다.The blowing agent (D) is cyclopentane and water. When the blowing agent is only cyclopentane, the foam obtained is likely to shrink. The usage-amount of a blowing agent is 0.1-30 mass% of cyclopentane, and 0.1-3 mass% of water with respect to a polyol.
본 발명에서는 전술한 것 이외의 첨가제를 사용할 수 있다. 이 첨가제로서는, 가소제, 충전제, 착색제, 난연제, 유기 또는 무기 충전제, 산화 방지제, 자외선 흡수제, 가소제, 안료·염료·항균제·항곰팡이제 등을 예로 들 수 있다. 본 발명에서는 난연제를 사용하는 것이 바람직하다. 난연제로서는, 트리에틸포스페이트, 트리스(β-클로로프로필)포스페이트 등의 인산 에스테르류, 아인산 에틸, 아인산 디에틸 등의 아인산 에스테르류의 인산 화합물 등을 예로 들 수 있다.In the present invention, additives other than those mentioned above can be used. As this additive, a plasticizer, a filler, a coloring agent, a flame retardant, an organic or inorganic filler, antioxidant, a ultraviolet absorber, a plasticizer, a pigment, a dye, an antibacterial agent, an antifungal agent, etc. are mentioned. In this invention, it is preferable to use a flame retardant. Examples of the flame retardant include phosphate compounds such as phosphate esters such as triethyl phosphate and tris (β-chloropropyl) phosphate, and phosphite esters such as ethyl phosphite and diethyl phosphite.
본 발명의 경질 폴리우레탄폼의 제조 방법의 구체적인 수순은, 전술한 이소시아네이트기 말단 프리폴리머를 함유하는 폴리이소시아네이트(A)와, 전술한 폴리올(B)을, 촉매(C), 발포제(D), 발포제(E), 및 그 외의 첨가제 등의 존재하에서, 후술하는 장치를 사용하여 혼합하고, 발포, 경화시키는 방법이다.The specific procedure of the manufacturing method of the rigid polyurethane foam of this invention uses the polyisocyanate (A) containing the above-mentioned isocyanate group terminal prepolymer, and the above-mentioned polyol (B), a catalyst (C), a foaming agent (D), and a foaming agent. In the presence of (E) and other additives, it is a method of mixing, foaming and curing using an apparatus described later.
본 발명에 의해 얻어지는 경질 폴리우레탄폼은, 우레탄 결합이나 우레아 결합과 같은 화학 결합을 가지는 것이다. 또한, 제조 조건에 따라서는, 발포시에 이소시아누레이트기를 생성시킬 수 있다. 이소시아누레이트기는, 이소시아네이트기를 촉매에 의해 3량화시켜 생성되고, 기계적 강도나 내열성 등을 향상시킬 수 있다.The rigid polyurethane foam obtained by this invention has a chemical bond like a urethane bond and a urea bond. Moreover, depending on manufacturing conditions, an isocyanurate group can be produced | generated at the time of foaming. An isocyanurate group is produced by trimerizing an isocyanate group with a catalyst, and can improve mechanical strength, heat resistance, etc.
이 때의 이소시아네이트 인덱스(전체 이소시아네이트기/전체 활성 수소기×100)는, 50∼800이며, 80∼300이 바람직하다.The isocyanate index at this time (all isocyanate groups / all active hydrogen groups x100) is 50-800, and 80-300 are preferable.
경질 폴리우레탄폼을 제조하는데 있어서는, 각 원료액을 균일하게 혼합 가능하면 어떠한 장치라도 사용할 수 있다. 예를 들면, 소형 믹서나, 일반적인 우레탄폼을 제조할 때 사용하는, 주입 발포용의 저압 또는 고압 발포기, 슬라브 발포용의 저압 또는 고압 발포기, 연속 라인용의 저압 또는 고압 발포기, 스프레이 공사용의 스프레이 발포기 등을 사용할 수 있다.In manufacturing a rigid polyurethane foam, any device can be used as long as it can mix each raw material liquid uniformly. For example, small mixers or low pressure or high pressure foamers for injection foam, slab foam low or high pressure foamers for use in the production of general urethane foam, low pressure or high pressure foamers for continuous lines, spray construction Spray foaming machine can be used.
본 발명에 의해 얻어지는 경질 폴리우레탄폼은, 후물 단열재로서 최적이지만, 이 외에도 보드, 패널, 냉장고, 차양, 도어, 덧문, 새시, 콘크리트계 주택, 욕조, 저온 탱크 기기, 냉동 창고, 파이프 커버, 합판에의 분사, 결로 방지, 슬라브 등, 각종 단열재 용도에 적용할 수 있다.The rigid polyurethane foam obtained by the present invention is optimal as a material insulation material, but in addition, boards, panels, refrigerators, sunshades, doors, shutters, chassis, concrete houses, bathtubs, low temperature tank equipment, refrigerated warehouses, pipe covers, and plywood It is applicable to various heat insulating material applications, such as spraying to a dew condensation prevention, slab, etc.
[실시예][Example]
이하, 본 발명을 실시예에 의해 더욱 상세하게 설명하지만, 본 발명은 이들로 한정되는 것은 아니다. 그리고, 실시예 및 비교예 중에서, 「%」는 「질량%」를 나타낸다.Hereinafter, although an Example demonstrates this invention still in detail, this invention is not limited to these. And in an Example and a comparative example, "%" represents the "mass%."
[경질 폴리우레탄폼용 폴리이소시아네이트의 합성][Synthesis of Polyisocyanate for Rigid Polyurethane Foam]
합성예 1Synthesis Example 1
교반기, 냉각관, 질소 도입관, 온도계를 구비한 반응기에, P-MDI(1)를 983kg 투입하고, 교반하면서 40℃에서 가온했다. 이어서, 1,2-PD를 5kg 투입하고, 교반하면서 80℃에서 4시간 반응시키고, 그 후, L-6900을 1.83kg, B-8466을 7.31kg 투입하고, 균일하게 혼합하여 경질 폴리우레탄폼용 폴리이소시아네이트 NCO-1을 얻었다. NCO-1의 NCO 함량은 30.1%였다. NCO-1의 외관에 있어서, 탁해지거나 침전은 확인되지 않았다.983 kg of P-MDI (1) was thrown into the reactor provided with the stirrer, the cooling tube, the nitrogen introduction tube, and the thermometer, and it heated at 40 degreeC, stirring. Subsequently, 5 kg of 1,2-PD was added and reacted at 80 ° C. for 4 hours while stirring. Then, 1.83 kg of L-6900 and 7.31 kg of B-8466 were added thereto, followed by uniformly mixing to form a polyurethane foam. Isocyanate NCO-1 was obtained. The NCO content of NCO-1 was 30.1%. In appearance of NCO-1, no turbidity or precipitation was observed.
합성예 2Synthesis Example 2
교반기, 냉각관, 질소 도입관, 온도계를 구비한 반응기에, MR-200을 983kg 투입하고, 교반하면서 40℃에서 가온했다. 이어서, 1,2-PD를 5kg 투입하고, 교반하면서 80℃에서 4시간 반응시켜서 경질 폴리우레탄폼용 폴리이소시아네이트 NCO-2를 얻었다. NCO-2의 NCO 함량은 30.2%였다. NCO-2의 외관에 있어서, 탁해지거나 침전은 확인되지 않았다.983 kg of MR-200 was thrown into the reactor provided with the stirrer, the cooling tube, the nitrogen introduction tube, and the thermometer, and it heated at 40 degreeC, stirring. Next, 5 kg of 1,2-PD was added and reacted at 80 ° C for 4 hours with stirring to obtain polyisocyanate NCO-2 for hard polyurethane foam. The NCO content of NCO-2 was 30.2%. In appearance of NCO-2, no turbidity or precipitation was observed.
합성예 3Synthesis Example 3
교반기, 냉각관, 질소 도입관, 온도계를 구비한 반응기에, MR-200을 983kg 투입하고, 교반하면서 40℃에서 가온했다. 이어서, L-6900을 1.83kg, B-8466을 7.31kg 투입하고, 균일하게 혼합하여 경질 폴리우레탄폼용 폴리이소시아네이트 NCO-3를 얻었다. NCO-3의 NCO 함량은 30.0%였다. NCO-3의 외관에 있어서, 탁해진 것이 확인되었다.983 kg of MR-200 was thrown into the reactor provided with the stirrer, the cooling tube, the nitrogen introduction tube, and the thermometer, and it heated at 40 degreeC, stirring. Subsequently, 1.83 kg of L-6900 and 7.31 kg of B-8466 were added and mixed uniformly to obtain polyisocyanate NCO-3 for hard polyurethane foam. The NCO content of NCO-3 was 30.0%. In appearance of NCO-3, it was confirmed that it was turbid.
합성예 1 내지 3에 있어서,In Synthesis Examples 1 to 3,
MR-200: 닛폰폴리우레탄공업사 제품 폴리머릭 MDIMR-200: polymeric MDI from Nippon Polyurethane Industries
상품명, 밀리오네이트(Millionate)(등록상표) MR-200 Brand name, Millionate (registered trademark) MR-200
이소시아네이트 함량 = 31.1%Isocyanate Content = 31.1%
MDI 함유량 = 40%MDI content = 40%
MDI 중의 4,4'-MDI 이외의 이성체 함유량 = 0.1%Isomer content other than 4,4'-MDI in MDI = 0.1%
25℃의 점성도 = 130mPa·s Viscosity at 25 ° C = 130 mPas
1,2-PD: 1,2-프로판디올1,2-PD: 1,2-propanediol
L-6900: 도오레·다우코닝사 제품 실리콘 정포제L-6900: Silicone Foaming Agent from Dow Corning
B-8466: 골드슈미트사 제품 실리콘 정포제B-8466: silicone foam stabilizer from Gold Schmidt
[폴리올프리믹스의 배합][Formulation of Polyol Premix]
이하에 나타내는 질량 배합비로 혼합하여, 폴리올프리믹스 OH-1,2를 얻었다.It mixed at the mass mix ratio shown below, and obtained polyol premix OH-1,2.
OH-1OH-1
폴리올-1: 60kg Polyol-1: 60 kg
폴리올-2: 20kg Polyol-2: 20 kg
폴리올-3: 5kg Polyol-3: 5 kg
폴리올-4: 15kg Polyol-4: 15 kg
CAT-11: 1.5kgCAT-11: 1.5 kg
CAT-12: 0.15kgCAT-12: 0.15kg
CAT-21: 0.3kgCAT-21: 0.3 kg
물: 1.9kg Water: 1.9kg
시클로펜탄: 16.1kg Cyclopentane: 16.1kg
OH-2OH-2
폴리올-1: 60kg Polyol-1: 60 kg
폴리올-2: 20kg Polyol-2: 20 kg
폴리올-3: 5kg Polyol-3: 5 kg
폴리올-4: 15kg Polyol-4: 15 kg
CAT-11: 1.5kgCAT-11: 1.5 kg
CAT-12: 0.15kgCAT-12: 0.15kg
CAT-21: 0.3kgCAT-21: 0.3 kg
물: 1.9kg Water: 1.9kg
시클로펜탄: 16.1kg Cyclopentane: 16.1kg
L-6900: 0.3kg L-6900: 0.3kg
B-8466: 1.2kg B-8466: 1.2 kg
상기 배합예에 있어서,In the combination example,
폴리올-1:Polyol-1:
슈크로스를 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어진 폴리에테르폴리올, 평균 관능기수 = 4.4, 수산기가 = 400mgKOH/g Polyether polyol obtained by addition of propylene oxide to an initiator having sucrose as a main component, average number of functional groups = 4.4, hydroxyl value = 400 mgKOH / g
폴리올-2:Polyol-2:
소르비톨을 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어진 폴리에테르폴리올, 평균 관능기수 = 5.0, 수산기가 = 460mgKOH/g Polyether polyol obtained by addition of propylene oxide to an initiator based on sorbitol, average number of functional groups = 5.0, hydroxyl value = 460 mgKOH / g
폴리올-3:Polyol-3:
글리세린을 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어진 폴리에테르폴리올, 평균 관능기수 = 3.0, 수산기가 = 1120mgKOH/g Polyether polyol obtained by addition of propylene oxide to an initiator containing glycerin as a main component, average number of functional groups = 3.0, hydroxyl value = 1120 mgKOH / g
폴리올-4:Polyol-4:
에틸렌디아민을 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어진 폴리에테르폴리올, 평균 관능기수 = 4.0, 수산기가 = 640mgKOH/gPolyether polyol obtained by addition of propylene oxide to an initiator containing ethylenediamine as a main component, average number of functional groups = 4.0, hydroxyl value = 640 mgKOH / g
CAT-11:CAT-11:
N,N-디메틸시클로헥실아민 N, N-dimethylcyclohexylamine
CAT-12:CAT-12:
펜타메틸디에틸렌트리아민 Pentamethyldiethylenetriamine
CAT-21:CAT-21:
트리스(디메틸아미노프로필)헥사하이드로-S-트리아진 Tris (dimethylaminopropyl) hexahydro-S-triazine
L-6900:L-6900:
도오레·다우코닝사 제품 실리콘 정포제 Doore Corning Products Silicone Foaming Agent
B-8466:B-8466:
골드슈미트사 제품 실리콘 정포제Gold Schmidt Silicone Foaming Agent
OH-1은 탁해지는 등의 외관 불량은 확인되지 않았지만, OH-2는 탁해진 것이 확인되었다.Appearance defects such as cloudiness of OH-1 were not confirmed, but cloudiness of OH-2 was confirmed.
[후물 단열재용 경질 폴리우레탄폼의 제조·평가][Manufacture and Evaluation of Rigid Polyurethane Foam for Thick Insulation]
실시예 1, 비교예 1, 비교예 2Example 1, comparative example 1, comparative example 2
NCO-1과 OH-1(실시예 1), NCO-2와 OH-2(비교예 1), NCO-3와 OH-1(비교예 2)의 조합에 의해, 이소시아네이트를 45℃ ± 1℃, 폴리올을 20℃ ± 1℃에서 조정한 후, 2.0리터의 폴리에틸렌제 비커에 이소시아네이트 인덱스 120으로 배합하고, 회전수 5000rpm으로 교반 믹서에 의해 수초동안 교반 혼합하고, 사전에 45℃에서 보온한 500×500×100mm의 알루미늄제 몰드 내에서, 실시예 1에서는 경화 시간을 3분, 비교예 1 및 비교예 2에서는 경화 시간을 3분, 4분, 5분으로 하여 몰드 발포를 행하고, 얻어진 폼에 대하여 경화특성을 확인하였다. 팩킹률은 130%로 하였다. 결과를 표 1에 나타낸다. Isocyanate is 45 ° C ± 1 ° C by the combination of NCO-1 and OH-1 (Example 1), NCO-2 and OH-2 (Comparative Example 1), and NCO-3 and OH-1 (Comparative Example 2) After adjusting a polyol at 20 degreeC +/- 1 degreeC, it mix | blends with an isocyanate index 120 in a 2.0-liter polyethylene beaker, stirring-mixing for several seconds with a stirring mixer at a rotation speed of 5000rpm, and heat-preserved at 45 degreeC 500x In a mold made of aluminum of 500 × 100 mm, in Example 1, the curing time was 3 minutes, and in the Comparative Examples 1 and 2, the curing time was 3 minutes, 4 minutes, and 5 minutes to mold foam, and the obtained foam was obtained. The curing characteristics were confirmed. The packing rate was 130%. The results are shown in Table 1.
비교예 3Comparative Example 3
밀리오네이트 MR-200(상기 기재)과 OH-2의 조합에 의해, 이소시아네이트를 45℃±1℃, 폴리올을 20℃ ± 1℃에서 조정한 후, 2.0리터의 폴리에틸렌제 비커에 이소시아네이트 인덱스 120으로 배합하고, 회전수 5000rpm으로 교반 믹서에 의해 수초동안 교반 혼합하고, 사전에 45℃에서 보온한 500×500×100mm의 알루미늄제 몰드 내에서, 경화 시간을 6분으로 하여 몰드 발포를 행하고, 얻어진 폼에 대하여 경화특성을 확인하였다. 팩킹률은 130%로 하였다.After adjusting the isocyanate at 45 ° C ± 1 ° C and the polyol at 20 ° C ± 1 ° C by the combination of milionate MR-200 (described above) and OH-2, the isocyanate index 120 was added to a 2.0-liter polyethylene beaker. The resulting foam was obtained by mixing and stirring at a rotational speed of 5000 rpm for several seconds with a stirring mixer, and in a mold of 500 × 500 × 100 mm aluminum previously heated at 45 ° C. with a curing time of 6 minutes. The curing characteristics were confirmed. The packing rate was 130%.
[표 1]TABLE 1
경화특성은, 몰드로부터 인출한 폼의 중앙부를 커팅하고, 폼 단면의 「갈라짐(금이 감)」이 확인되지 않은 것을 합격, 「갈라짐」이 확인된 것을 불합격으로서 평가했다.The hardening characteristic cut | disconnected the center part of the foam taken out from the mold, and evaluated that the "cracking" of the cross section of the foam was not confirmed, and that "cracking" was confirmed as rejection.
경화특성에 있어서, 실시예 1의 처방은 경화 시간 3분으로 한 것에서도, 폼 단면의 「갈라짐」은 확인되지 않고, 양호한 경화특성을 나타낸다. 또한, 열전도율도 양호하였다.In hardening characteristic, even if it made the prescription of Example 1 into hardening time 3 minutes, "cracking" of a foam cross section is not recognized, and shows favorable hardening characteristic. In addition, the thermal conductivity was also good.
비교예 1의 처방에 있어서는, 경화 시간 3분으로는, 폼 단면에 「갈라짐」이 확인되었으므로, 경화특성은 불합격이며, 경화 시간을 4분으로 하면, 폼 단면에 미세한 「갈라짐」이 확인되었으므로, 경화특성은 불합격이며, 경화 시간 5분에 겨우 경화특성이 합격되었다. 이 비교예의 처방에서는, 실시예의 처방과 비교하면 생산성이 매우 낮다고 볼 수 있다.In the prescription of the comparative example 1, since the "cracking" was confirmed by the cross section of a foam in 3 minutes of hardening time, hardening characteristic is disqualified, and when the hardening time is made into 4 minutes, fine "cracking" was confirmed by a foam cross section, The hardening characteristic was disqualified, and hardening characteristic was only passed in 5 minutes of hardening time. In the prescription of this comparative example, productivity can be considered very low compared with the prescription of an Example.
비교예 2의 처방에서는, 미변성된 폴리머릭 MDI와 정포제를 사전에 혼합한 것을 사용하였으므로, 거품이 균일하게 폼 내에 분산되어 있지 않으므로, 열전도율이 좋지 못하다. 또한, 경화특성도 실시예와 비교하여 불충분하였다.In the prescription of the comparative example 2, since the unmodified polymeric MDI and the foam stabilizer were mixed previously, since foam is not uniformly disperse | distributed in a foam, thermal conductivity is not good. In addition, the curing characteristics were also insufficient compared with the examples.
비교예 3에 있어서는, 경화 시간을 6분으로 상당히 길게 했음에도 불구하고, 폼 단면에 「갈라짐」이 확인되었으므로, 경화특성은 불합격이었다. 또한, 폴리올프리믹스와 시클로펜탄의 상용성이 불충분하므로, 거품이 균일하게 폼 내에 분산되어 있지 않으므로, 열전도율이 좋지 못하였다. 이 처방에서는, 전술한 비교예 1과 비교해도 생산성이 매우 낮다고 볼 수 있다.In the comparative example 3, although the hardening time was considerably lengthened by 6 minutes, since the "cracking" was confirmed by the foam cross section, hardening characteristic was disqualified. In addition, since the compatibility between the polyol premix and the cyclopentane was insufficient, since the foam was not uniformly dispersed in the foam, the thermal conductivity was not good. In this prescription, it can be said that productivity is very low compared with the comparative example 1 mentioned above.
Claims (1)
폴리이소시아네이트(A)가, 폴리머릭 MDI(A1-1)와, 측쇄 알킬기를 가지는 저분자 폴리올(A1-2)을 반응시켜 생성한 이소시아네이트기 함유 프리폴리머(A1) 및 정포제(A2)를 함유하고,
폴리올(B)이, 이하의 폴리올(B1∼B4)를 함유하고,
촉매(C)가, 우레탄화 촉매(C1)와 3량화 촉매(C2)를 함유하고,
발포제(D)가 시클로펜탄(D1) 및 물(D2)을 병용하는, 후물 단열재용 경질 폴리우레탄폼의 제조 방법:
폴리올(B1):
슈크로스를 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어지고, 평균 관능기수 = 3∼6, 수산기가 = 300∼600 mgKOH/g인 폴리에테르폴리올
폴리올(B2):
소르비톨을 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어지고, 평균 관능기수 = 3∼6, 수산기가 = 300∼600 mgKOH/g인 폴리에테르 폴리올
폴리올(B3):
글리세린을 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어지고, 평균 관능기수 = 2∼4, 수산기가 = 10001500 mgKOH/g인 폴리에테르 폴리올
폴리올(B4):
에틸렌 디아민을 주성분으로 하는 개시제에 프로필렌옥사이드의 부가에 의해 얻어지고, 평균 관능기수 = 3∼5, 수산기가 = 400∼800 mgKOH/g인 폴리에테르 폴리올.In the manufacturing method of the rigid polyurethane foam for thick insulation materials which makes polyisocyanate (A) and polyol (B) react and foam in presence of a catalyst (C) and a foaming agent (D),
The polyisocyanate (A) contains an isocyanate group-containing prepolymer (A1) and a foam stabilizer (A2) produced by reacting a polymeric MDI (A1-1) with a low molecular polyol (A1-2) having a side chain alkyl group,
The polyol (B) contains the following polyols (B1 to B4),
Catalyst (C) contains a urethanization catalyst (C1) and a trimerization catalyst (C2),
Process for producing rigid polyurethane foam for thick insulation material, in which the blowing agent (D) uses cyclopentane (D1) and water (D2) together:
Polyol (B1):
Polyether polyol obtained by addition of propylene oxide to an initiator having sucrose as a main component and having an average number of functional groups = 3 to 6 and a hydroxyl group = 300 to 600 mgKOH / g
Polyol (B2):
Polyether polyol obtained by addition of propylene oxide to an initiator containing sorbitol as a main component and having an average number of functional groups = 3 to 6 and a hydroxyl group = 300 to 600 mgKOH / g
Polyol (B3):
Polyether polyol obtained by addition of propylene oxide to an initiator having glycerin as a main component, and having an average number of functional groups = 2 to 4 and a hydroxyl value = 10001500 mgKOH / g
Polyol (B4):
Polyether polyol obtained by addition of propylene oxide to the initiator which has ethylene diamine as a main component, and whose average number of functional groups is 3-5, and hydroxyl value is 400-800 mgKOH / g.
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Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08120048A (en) * | 1994-10-19 | 1996-05-14 | Nippon Polyurethane Ind Co Ltd | Polyisocyanate composition for rigid foam and production of rigid polyurethane foam using the same |
JP3389588B2 (en) * | 1994-12-28 | 2003-03-24 | 日本ポリウレタン工業株式会社 | Method for producing rigid polyurethane foam using polyisocyanate mixture for rigid foam |
JP3191681B2 (en) * | 1995-09-07 | 2001-07-23 | 日本ポリウレタン工業株式会社 | Soil-stabilized polyurethane foam resin composition and soil stabilization method using the composition |
JPH09165427A (en) * | 1995-12-14 | 1997-06-24 | Mitsui Toatsu Chem Inc | Rigid polyurethane foam and its production |
JPH10182776A (en) * | 1996-12-25 | 1998-07-07 | Mitsui Chem Inc | Production of rigid polyurethane foam |
JP2001310925A (en) * | 2000-04-27 | 2001-11-06 | Toyo Tire & Rubber Co Ltd | Production method of hard polyurethane foam with flame resistance |
JP2006291124A (en) * | 2005-04-14 | 2006-10-26 | Toyo Tire & Rubber Co Ltd | Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam |
JP2007191679A (en) * | 2005-12-21 | 2007-08-02 | Kao Corp | Method for producing polyurethane foam |
JP2008260842A (en) * | 2007-04-12 | 2008-10-30 | Nippon Polyurethane Ind Co Ltd | Polyisocyanate composition for rigid polyurethane foam made by foaming using cyclopentane, and method for producing rigid polyurethane foam by using the same |
JP5311267B2 (en) * | 2007-04-12 | 2013-10-09 | 日本ポリウレタン工業株式会社 | Polyisocyanate composition for rigid polyurethane foam for foaming cyclopentane and method for producing rigid polyurethane foam using the same |
-
2008
- 2008-01-31 JP JP2008021676A patent/JP5333981B2/en active Active
- 2008-11-14 WO PCT/JP2008/003320 patent/WO2009095964A1/en active Application Filing
- 2008-11-14 KR KR1020107015017A patent/KR20100100951A/en not_active Application Discontinuation
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KR101634309B1 (en) * | 2015-02-27 | 2016-06-30 | (주)엠피텍 | Rigid polyurethane spray foam composition of low density |
KR20170026082A (en) | 2016-04-01 | 2017-03-08 | 정우화인 주식회사 | Method and Apparatus for Producing Excellent Heat Insulating Polyurethane Foam Board |
KR102053658B1 (en) | 2019-04-11 | 2020-01-17 | 주식회사 정우산업 | Method and Apparatus for Producing Excellent Flame Retardant Polyurethane Foam Board |
KR102026626B1 (en) | 2019-05-14 | 2019-09-30 | 정우화인 주식회사 | Method of Producing Excellent Flame Retardant Polyurethane Foam Board |
KR102132638B1 (en) | 2019-09-06 | 2020-07-21 | 김유석 | Automatic supply apparatus of inorganic filler for producing excellent flame retardant polyurethane foam board |
KR102141961B1 (en) | 2019-12-31 | 2020-08-06 | 주식회사 정우산업 | Method of Manufacturing Quasi-incombustible Polyurethane Board |
KR20210085732A (en) | 2019-12-31 | 2021-07-08 | 화인케미칼 주식회사 | Hybrid polyurethane foam capable of shielding electromagnetic waves using a mold carrier and its manufacturing method |
Also Published As
Publication number | Publication date |
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JP5333981B2 (en) | 2013-11-06 |
WO2009095964A1 (en) | 2009-08-06 |
JP2009179752A (en) | 2009-08-13 |
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