CN111136851B

CN111136851B - High-strength corrosion-resistant product and preparation method thereof

Info

Publication number: CN111136851B
Application number: CN201911413300.1A
Authority: CN
Inventors: 林孝发; 林孝山; 李�浩; 李伟宇; 李日红
Original assignee: Jomoo Kitchen and Bath Co Ltd
Current assignee: Jomoo Kitchen and Bath Co Ltd
Priority date: 2019-12-31
Filing date: 2019-12-31
Publication date: 2021-10-26
Anticipated expiration: 2039-12-31
Also published as: CN111136851A

Abstract

The invention discloses a preparation method of a high-strength corrosion-resistant product. The high-strength corrosion-resistant product comprises a thermosetting resin and a metal wrapped in the thermosetting resin; the surface of the thermosetting resin is dense and has cells inside, And the cell size is gradually reduced from the inner surface in contact with the metal surface to the outer surface of the resin from the inside to the outside. The product of the invention has strong pressure resistance, strong corrosion resistance and easy cleaning.

Description

High-strength corrosion-resistant product and preparation method thereof

Technical Field

The invention relates to a high-strength corrosion-resistant product and a preparation method thereof.

Background

The bathroom floor drain material is mainly made of metal materials such as stainless steel, copper-zinc alloy and the like and plastic materials, wherein the common plastic (PP/ABS/PVC) floor drain has poor texture, low density, and no high temperature resistance or scratch resistance; stainless steel floor drains and electroplated floor drains are not resistant to acid corrosion and are easy to rust; the surface treatment process (spraying and the like) of the metal material is easy to fall off.

To above problem, the body floor drain is produced by:

1. high performance thermoplastic materials: polyphenylene Sulfide (PPS), Polyoxymethylene (POM), tetramethylene terephthalate (PBT), and the like; the high-performance thermoplastic materials have excellent performance, but have the defects of poor texture, strong plastic texture, general impact resistance, high energy consumption and the like;

2. special ceramic floor drain: such as zirconia ceramic floor drains; however, they have low strength, poor impact resistance, insufficient stain resistance, large energy consumption, and the like.

3. Other thermosetting materials: after injection molding or die pressing, the brittleness is high, the strength is low, the stain resistance is poor, the appearance quality is poor and the like.

Disclosure of Invention

The invention mainly aims to provide a high-strength (compression-resistant) corrosion-resistant product.

The technical scheme adopted by the invention for solving the technical problem is as follows:

a preparation method of a high-strength corrosion-resistant product comprises the following steps:

1) processing a metal sample into a desired shape;

2) preparing a resin raw material into to-be-foamed bulk composite resin, forming a to-be-foamed bulk resin-metal-to-be-foamed bulk resin sandwich structure, and putting the to-be-foamed bulk resin sandwich structure into a mold; wherein the resin raw material comprises unsaturated polyester and a foaming agent, and the foaming temperature of the foaming agent is higher than the lowest thermosetting molding temperature of the unsaturated polyester;

3) the mould is closed and heated to cure and form the composite resin, and the metal is heated in the process by adopting a mode including electromagnetic heating, wherein the heating temperature of the mould is lower than the heating temperature of the metal and is equal to or higher than the lowest thermosetting forming temperature of the unsaturated polyester; the heating temperature of the metal is equal to or greater than the foaming temperature of the foaming agent.

Preferably, the foaming temperature of the blowing agent is higher than the lowest thermosetting molding temperature of the unsaturated polyester and lower than the highest thermosetting molding temperature of the unsaturated polyester.

Preferably, the heating temperature of the metal is 0.1 to 10 ℃ higher than the foaming temperature of the foaming agent.

In the invention, the high-strength corrosion-resistant product comprises at least one of a floor drain, a basin, a storage rack, a urinal and the like.

Preferably, the metal comprises at least one of iron or stainless steel.

Preferably, the resin raw materials comprise, by mass:

30% -50% of unsaturated polyester; 20-40% of reinforcing fiber, and foaming agent: 0.5 to 4 percent;

gas-phase white carbon black: 0.5 to 1.5 percent; fluorine-containing compound: 1% -8%; thickening agent: 0.05% -0.1%;

1% -8% of low shrinkage agent: initiator: 0.5% -3%; 1.5 to 3 percent of other auxiliary agents;

the balance of inorganic modified filler;

wherein, the unsaturated polyester comprises one or the combination of ortho-benzene type, meta-benzene type, bisphenol A type and neopentyl glycol type;

the inorganic modified filler comprises at least one of calcium carbonate, barium sulfate, hydrated alumina and nano ceramic powder, and the particle size is 200-800 meshes;

the reinforced fiber comprises at least one of glass fiber/carbon fiber/aramid fiber, and the thickness of the reinforced fiber is 4-10 mm;

the foaming agent is at least one of core-shell polymer, Azodicarbonamide (AC) and supercritical gas; the supercritical gas can be carbon dioxide or nitrogen.

Fumed silica with particle size of 5-800 nm;

fluorine-containing compound: comprises at least one of methacrylic acid fluorine-containing ester and fluorosilane;

in a preferred embodiment of the present invention,

the thickener comprises at least one of calcium hydroxide and magnesium oxide;

the low shrinkage agent comprises at least one of PMMA (polymethyl methacrylate)/PE (polyethylene)/PS (polystyrene);

the initiator is peroxide;

other auxiliary agents comprise at least one of polymerization inhibitor, internal release agent, colorant and the like;

the inorganic filler comprises at least one of calcium carbonate, barium sulfate, hydrated alumina and nano ceramic powder.

Preferably, the metal is fixed in a mold, wherein the mold upper/lower mold has an electromagnetic heating device that can perform space heating of the metal insert module embedded in the resin.

Preferably, the mold is evacuated and maintained for 50s to 300s while heating the metal and the resin.

Preferably, in the step 2), the resin is prepared into the to-be-foamed dough-shaped composite resin, and the to-be-foamed dough-shaped resin sandwich structure is formed and put into a mould.

Preferably, the preparation method of the dough-like composite resin to be foamed comprises the following steps:

(1) mixing and kneading: uniformly mixing and stirring unsaturated polyester for 4-6h, adding raw materials including filler, hydrophobic fumed silica, initiator/polymerization inhibitor and glass fiber, mixing and kneading for 5-15min, controlling the temperature to be less than or equal to 30 ℃, and preparing uniform bulk resin;

(2) foaming and kneading: and (3) immediately and slowly adding a foaming agent and other resin components into the bulk resin, and further kneading the mixture for 3-5min by using a kneader to prepare the bulk composite resin to be foamed.

Preferably, the foaming agent is selected from core-shell polymers and is subjected to the following surface treatment: spraying silane coupling agent on the surface of the core-shell polymer, stirring uniformly, quantitatively soaking the treated core-shell polymer into a polyester system, uniformly dispersing by adopting ultrasonic waves, and stirring for 10-20min, wherein the temperature is controlled to be less than or equal to 30 ℃.

The conventional heating method of thermosetting resin is to carry out heat transfer molding from outside to inside, and aims at solving the problems that small molecules are separated out to release gas in the curing process of an upper die and the problems of poor surface quality, serious gas mark, pollution resistance, poor corrosion resistance and the like easily occur when the material is subjected to the traditional heating treatment mode; meanwhile, the invention adopts a microporous foaming structure to realize a double sandwich structure, so that the cost is saved, the density is reduced, and the toughness and the shock resistance of the material can be improved. The principle is as follows:

1. micro-nano pore foaming structure-toughening:

the microporous structure can produce a large amount of silver veins when the product receives the impact, and a large amount of energy can be absorbed to this process, slows down the injury that the impact brought: when the micropores are uniformly distributed in the material, the stress field is not uniform, the force at the impact point can be consumed to other micropore structures through the micro-nano pore structure, a large amount of silver lines are gradually generated, the stress diffusion is stopped, destructive cracks or cracking cannot be generated, and the macroscopic expression means that when the material is impacted by external force or high and low temperature internal stress, the material can be self-digested and buffered, the toughness is enhanced, the phenomena of product cracking and the like cannot be generated; the core-shell polymer is preferably selected, so that the phenomenon that AC or supercritical gas forms nucleation points on the surface of the glass fiber to form defects is avoided;

2. double "sandwich" structure-toughening/cost/density reduction:

embedded heating metal structure, inside and outside heating unit simultaneous working impels inside foaming earlier shaping, surface crust, constructs the foam sandwich structure: the curing temperature of the upper/lower die is lower than the foaming temperature, the upper/lower surface is not foamed, the upper/lower surface is subjected to skinning and shaping after being slowly leveled, the surface skinning is compact and uniform, the interior is foamed from inside to outside, the size of the foam hole is gradually reduced from inside to outside to form a sandwich structure, meanwhile, a metal structure is embedded, thermosetting modified resin is coated outside the foam hole, and the overall structure of the more stable sandwich structure is more stable;

3. surface skinning-stain/corrosion/gas mark improvement:

the temperature of the upper die and the lower die is lower than the expansion temperature (namely the foaming temperature) of the foaming material, the bulk resin has strong fluidity in the die pressing process, is flatly spread under the pressure of the die and is cured and molded, the surface is compact and uniform, and the defects of serious pressure marks and the like of the traditional die are obviously improved; meanwhile, because the thickness of the product is larger, the inner curing speed is slow or the inner cracking is generated due to no curing when the upper die and the lower die are heated, and the curing process can effectively solve the problem;

the product of the invention has excellent corrosion resistance, high strength, good surface quality, low density and low cost; the strength and impact resistance of the product can be better improved by adopting the core-shell polymer microcellular foaming structure, the strength and bearing capacity of the product can be obviously improved by adopting a metal embedded structure heating mode, and the surface defect, the product quality and the corrosion resistance and corrosion resistance of the product can be improved by the preparation process.

Drawings

The invention is further illustrated by the following figures and examples.

FIG. 1 is a schematic diagram of the principles of the present invention;

FIG. 2 is a comparative drawing of the floor drain product of example 1 (left) and the existing floor drain product (right)

Detailed Description

Example 1

Taking a floor drain product as an example, the technical scheme of the invention is as follows:

the basic scheme comprises the following formula:

40% of unsaturated polyester: AROPOL MR14029 resin

The balance of inorganic modified filler: barium sulfate

30% of glass fiber: thai glass fiber Limited, glass fiber length 5mm-8mm

Core-shell polymer blowing agent: 2%: PG16 foaming agent, Beijing Shanghai brocade science and technology Limited

Gas-phase white carbon black: 1%: hydrophobic fumed silica of Yingchuangdegussa

Fluorine-containing methacrylic acid ester: 5%: aldrich Co of USA

Thickening agent: 0.1% magnesium oxide

Low shrinkage agent: PMMA/PE/PS, PMMA was used in this example at a level of 5%

Initiator: TBPB tert-butyl peroxybenzoate, 1.5%; purchased from Akema, TBPO peroxy-2-ethylhexoate, 1.5%, and purchased from Aksu

1.5 percent of other auxiliary agents

A heat-conducting metal structure: stainless steel, iron, etc., and is formed by stamping or casting, and the thickness is 0.5mm

The preparation method comprises the following steps:

1) surface treatment of the core-shell polymer: spraying a silane coupling agent on the surface of the core-shell polymer, quantitatively soaking the treated core-shell polymer into an unsaturated polyester system after uniformly stirring, uniformly dispersing and stirring for 15min by adopting ultrasonic waves, and controlling the temperature to be less than or equal to 30 ℃;

2) and (3) surface treatment of fumed silica: adding fumed silica into deionized water, stirring uniformly, adding 10-20% of silane coupling agent, heating, fully performing reflux reaction, and baking in an oven at 100 ℃ to prepare hydrophobic modified fumed silica;

3) mixing and kneading: uniformly mixing and stirring unsaturated polyester for 5 hours, adding filler (the water content is less than or equal to 0.1 percent), hydrophobic fumed silica, initiator/polymerization inhibitor, glass fiber (the water content is less than or equal to 0.1 percent) and the like, mixing and kneading for 10 minutes, controlling the temperature to be less than or equal to 30 ℃, and preparing uniform bulk resin;

4) foaming and kneading: slowly adding the core-shell polymer and resin system dispersed in the step 1) into the bulk resin (uniformly adding), further kneading for 4min by adopting a kneader to finish preparing the bulk composite resin to be foamed, and storing at 25 ℃;

5) forming a metal sample sheet: punching and forming a metal sample to prepare an embedded structure module;

6) surface treatment of the metal embedded module: carrying out surface roughening treatment on the metal embedded structure module by adopting a sand blasting/chemical etching process, then carrying out ultrasonic cleaning, and carrying out pretreatment in a high-temperature oven for more than 1 h;

7) compression molding: the mould preheats, will wait to foam bulk resin, metal embedding module, wait to foam bulk resin and put into the mould fixedly (sandwich structure) in proper order, and wherein metal embedding module can be fixed to in the mould, and the upper/lower mould of mould has electromagnetic heating device, can separate empty heating to the metal embedding module of embedding into in the resin. Then, the mould and the metal are heated to the thermosetting molding temperature of the resin, and then the metal temperature is independently raised by 5-20 ℃ by utilizing an electromagnetic heating device. Exhausting and maintaining the pressure for 50-300 s;

8) and (3) flash treatment: taking out and cooling the product and then carrying out flash treatment.

Results

The floor drain has good corrosion resistance/good hydrophobicity, is not easy to be corroded and polluted by the external environment, has high strength, good impact resistance and easy cleaning of drainage, has great product performance advantage compared with the traditional stainless steel floor drain, adopts a mould pressing or injection molding process, has strong designability of product structure and designable appearance color, and has the performance which can not be achieved by stainless steel or metal floor drains;

example 2

Taking a urinal product as an example, the technical scheme of the invention is as follows:

the basic scheme comprises the following formula:

45% of unsaturated polyester: AROPOL MR14029 resin

Inorganic modified filler: the balance of barium sulfate%

18% of glass fiber: 4-6mm of Taian glass fiber Co

Core-shell polymer blowing agent: 0.5%: PG18 foaming agent of Beijing Shanghai brocade science and technology Limited

Gas-phase white carbon black: 1.5%: hydrophobic fumed silica of Yingchuangdegussa

Fluorine-containing methacrylic acid ester: 3.5%: aldrich Co of USA

Thickening agent: 0.08% of calcium hydroxide and magnesium oxide

Low shrinkage agent: PMMA

Initiator: TBPB tert-butyl peroxybenzoate, 1.5% from Achima, TBPO tert-butyl peroxy-2-ethylhexanoate, 1.5% from Acksu;

1.5 percent of other auxiliary agents

A heat-conducting metal structure: stamping and molding stainless steel with the thickness of 1.5mm

The preparation method comprises the following steps:

2) and (3) surface treatment of fumed silica: adding fumed silica into deionized water, stirring uniformly, adding 10-20% of silane coupling agent, heating, carrying out reflux reaction, and baking in an oven at 100 ℃ to prepare hydrophobic modified fumed silica;

4) foaming and kneading: slowly adding the core-shell polymer and resin system dispersed in the step 1 into the bulk resin (uniformly adding), further kneading for 4min by adopting a kneader to finish preparing the bulk composite resin to be foamed, and storing at 25 ℃;

5) forming a metal sample sheet: punching a metal sample to prepare an embedded structure module, and processing a welding support structure for installation on a wall surface;

7) compression molding: the mould preheats, will wait to foam bulk resin, metal embedding module, wait to foam bulk resin and put into the mould fixedly (sandwich structure) in proper order, wherein metal embedding module can be fixed to in the mould, wherein the mould is gone up/lower mould and is had electromagnetic heating device, can separate empty heating to the metal embedding module of embedding into in the resin. Then, the mould and the metal are heated to the thermosetting molding temperature of the resin, and then the metal temperature is independently raised by 5-20 ℃ by utilizing an electromagnetic heating device. Exhausting and maintaining the pressure for 50-300 s;

The urinal made of the material has the advantages of low product density, high impact resistance, difficult crushing, convenient transportation, good hydrophobicity, easy cleaning, good corrosion resistance, difficult corrosion and rusting, and obvious comprehensive performance advantage compared with common ceramic urinals and stainless steel urinals; simultaneously, compared with stainless steel urinals and ceramic urinals, the material has a series of advantages of better dimensional stability, strong designability of color, low production energy consumption and the like.

Claims

1. a preparation method of a high-strength corrosion-resistant product, comprising the steps:

1) Process the metal sample into the desired shape;

2) The resin raw material is prepared into a lump-shaped composite resin to be foamed, and a sandwich structure of lump-shaped resin to be foamed-metal-to-be-foamed lump-shaped resin is formed into the mold; wherein, the resin raw material includes unsaturated polymer; Ester and blowing agent, and the foaming temperature of the blowing agent is greater than the minimum thermosetting temperature of the unsaturated polyester;

3) The mold is closed and heated to solidify the composite resin. In this process, the metal is heated by means of electromagnetic heating, wherein the heating temperature of the mold is lower than the heating temperature of the metal, and is equal to or higher than the unsaturated polyester. The minimum thermosetting temperature is the lowest; the heating temperature of the metal is equal to or greater than the foaming temperature of the foaming agent; the temperature of the upper and lower molds is lower than the foaming temperature of the foaming material.

2. the preparation method of a kind of high-strength corrosion-resistant product as claimed in claim 1 is characterized in that: the foaming temperature of foaming agent is higher than the minimum thermosetting temperature of unsaturated polyester, and is lower than unsaturated polyester. Maximum thermosetting temperature for esters.

3 . The method for preparing a high-strength corrosion-resistant product according to claim 1 , wherein the heating temperature of the metal is 0.1-10° C. higher than the foaming temperature of the foaming agent. 4 .

4 . The method for preparing a high-strength corrosion-resistant product according to claim 1 , wherein the heating temperature of the metal is 5-20° C. higher than the heating temperature of the mold. 5 .

5. the preparation method of a kind of high-strength corrosion-resistant product according to claim 1, is characterized in that: described resin raw material comprises by mass ratio:

Unsaturated polyester: 30%-50%; Reinforcing fiber: 20%-40%, Foaming agent: 0.5%-4%;

Fumed silica: 0.5% to 1.5%; fluorine-containing compounds: 1% to 8%; thickener: 0.05% to 0.1%;

Low shrinkage agent: 1%～10%; Initiator: 0.5%～3%; Other additives: 1.5%～3%;

Inorganic modified filler: balance;

Wherein, described unsaturated polyester comprises at least one in o-benzene type, m-benzene type, bisphenol A type, neopentyl glycol type;

The inorganic modified filler includes at least one of calcium carbonate, barium sulfate, hydrated alumina, and nano-ceramic powder, and the particle size is 200 mesh to 800 mesh;

The reinforcing fiber includes at least one of glass fiber/carbon fiber/aramid fiber, and the length is 4-10mm;

The foaming agent is at least one of core-shell polymer, azodicarbonamide, and supercritical gas;

Fumed silica, particle size 5-800nm;

Fluorine-containing compound: including at least one of methacrylic acid fluorine-containing ester and fluorosilane.

6. the preparation method of a kind of high-strength corrosion-resistant product according to claim 5 is characterized in that:

The thickener includes at least one of calcium hydroxide and magnesium oxide;

The low shrinkage agent includes at least one of PMMA/PE/PS;

The initiator is at least one of peroxide, styrene, methyl methacrylate, and dipropylene phthalate;

Other auxiliary agents include at least one of polymerization inhibitor, internal mold release agent, and colorant;

The inorganic filler includes at least one of calcium carbonate, barium sulfate, hydrated alumina, and nano-ceramic powder.

7. The preparation method of a high-strength corrosion-resistant product according to claim 1, wherein the metal is fixed in the mold, wherein the upper/lower mold of the mold has the ability to isolate the metal embedded module embedded in the resin. Air heating electromagnetic heating device.

8 . The method for preparing a high-strength corrosion-resistant product according to claim 1 , wherein when the metal and resin are heated, the mold is exhausted for 0.5s-3s, and then the mold is closed for 50s-300s. 9 .

9. the preparation method of a kind of high-strength corrosion-resistant product according to claim 1, is characterized in that:

The preparation method of the bulk composite resin to be foamed comprises:

(1) Kneading and kneading: The polyester system is uniformly mixed and stirred for 4-6 hours, and raw materials including filler, hydrophobic gas-phase silica, initiator/inhibitor, and glass fiber are added for mixing and kneading for 5-15 minutes. Control ≤30℃ to prepare uniform lump resin;

(2) Foaming and kneading: The foaming agent and other resin components are immediately and slowly added to the above-mentioned lump resin, and further kneaded by a kneader for 3-5 minutes to prepare the lump composite resin to be foamed.

10. The preparation method of a high-strength corrosion-resistant product according to claim 5, wherein the foaming agent adopts a core-shell polymer, and is treated as follows: the surface of the core-shell polymer is sprayed with a silane coupling agent, After stirring evenly, the treated core-shell polymer is quantitatively soaked into the polyester system, and is uniformly dispersed by ultrasonic waves, stirred for 10-20 minutes, and the temperature is controlled to be ≤30°C.